Vous êtes sur la page 1sur 323

M.SC.

(FINAL) CHEMISTRY

PAPER –IV : ORGANOTRANSITION METAL CHEMISTRY

BLOCK-I

Unit -1 : Alkyls and Aryls of Transition Metals

Unit-2 : Compounds of Transition Metal- Carbon


Multiple Bonds

Unit – 3 : Transition Metal  - Complexes

Author – Dr. Purushottam B. Chakrawarti


Editor – Dr. Anuradha Mishra

1
M.Sc (Final) CHEMISTRY
Paper-4: ORGANOTRANSIONAL METAL
BLOCK – I : SUMMARY

This block includes three units.

Unit-1: Alkyls and aryls of transition metals discusses nomenclature,


types and classification and methods of preparation of alkyl and
aryl complexes of metals, along with their stability, their
decomposition pathways and characteristic reactions. In the end of
the unit uses of organo-copper in organic synthesis is also
discussed.

Unit-2: Compounds of transition metal-Carbon multiple bonds,


presents study of alkylidene, alkylidyne and Fisher carbenes. The
unit ends with analysis of various applications of these compounds
in organic synthesis.

Unit-3: Transition metal  Complex-I, describes preparation, structures


and bonding in 2-hapto and 3-hapto complexes. At the end of the
unit applications of these complexes in organic synthesis are also
described.

2
UNIT-1 ALKYLS AND ARYLS OF TRANSITION METALS
STRUCTURE

1.1 Introduction

1.2 Objectives

1.3 Metal Alkyls and Aryls

1.3.1 Nomenclature

1.3.2 Classification and Types

1.3.3 Routes of Synthesis

Hydrocarbyls of Group=3 (d1 – Metals)

Hydrocabrbyls of Group -4 (d2 – Metals)

Hydrocarbyls of Group-5 (d3 – Metals)

Hydrocarbyls of Group – 6 (d4 – Metals)

Hydrocarbyls of Group -7 (d5 – Metals)

Hydrocarbyls of Group 8, 9 and 10 (d6, d7 and d8 – Metals)

1.3.4 Stability

1.3.5 Decomposition Pathways

1.4 Organo-Copper in Organic Synthesis

1.5 Let Us Sum Up

1.6 Check Your Progress : The key

3
1.1 INTRODUCTION

Organometallic Compounds are Organic Compounds of metals. In these


compounds metal- carbon bond is present. These compounds have ionic or
covalent, localised or delocalised bonding between one or more carbon atoms
of organic – group or molecule and transition lanthanide, actinide- or main
group metal-atom. Because organic compounds are hydrocarbon or their
derivatives, hence in organometallic compounds, generally, those compounds
are included in which one or more hydrocarbon radical(s) are directly linked
with metal atom. In this respect metal-carbides, metal carbonates, metal
cyanides, metal carboxylates (and also metal carbonyls) should not be included
in organo metallic compounds, Metal carbonates and metal carboxylates are not
organometallic compounds, as they do not have metal- carbon bond. While,
although metal- carbides and metal- cyanides have metal-carbon bond, they are
not organic compounds. As a matter of fact, organometallic chemistry functions
as a bridge between organic and inorganic chemistry.

In this unit we shall discuss nomenclature, types and classification and


methods of preparation of alkyl and aryl compounds of various metals. In the
end of the unit we shall discuss the stability, decomposition pathways and
characteristic reactions of these compounds, along with the use of organo
copper in organic synthesis.

4
1.2 OBJECTIVES

The main objective of this unit is to give all the necessary information
about alkyl and aryl compounds of transition metals. After going through this
unit you should be able to :
 know what are metal-alkyls and metal-aryls,
 understand how they are named,
 describe classification and types of alkyls and aryls of transition metals,.
 discuss methods of synthesis of hydrocarbyls of different groups of
transition metals.
 explain stability, decomposition pathway, and characteristic reactions of
transition metal-hydrocarbyls, and
 discuss the importance of organo-copper compounds in organic-
synthesis.

1.3 METAL ALKYLS AND ARYLS

Compounds of metals with alkyl radicals are called 'metal alkyls', while
those with aryl radicals are known 'Metal aryls'.

Although (Me3 PtI)4 was synthesised in 1907, but for a long time it was
considered that the   bonded transition metal alkyl and aryls tend to be rather
unstable compared to their main group analogues. This inference was drawn
from the fact, diethyl iron (II) and diethyl cobalt (II) could not be prepared by
the action of metal bromide with ethyl magnesium bromide. As a matter of fact
metal-carbon bond in transition metal alkyls is not less stable compared to that
present in main group metal alkyls. But, while in main groups M-C bond-
strength regularly decreases, the bond strength gradually increases with increase

5
in atomic number. (Table 1.1). In this respect, the compounds of first transition
metal series will be least stable thermodynamically. As a matter of the difficulty
in making metal-carbon bond, is not due to thermodynamic but due to kinetic
aspect. Which makes their synthesis difficult.

Table 1.1
Enthalpies, D KJ mol-1 of Metal Carbon bond Dicomposition
Complex Enthalpy
Ti (CH2 CMe3)4 198
Zr (CH2 CMe3)4 249
Hf (CH2 CMe3)4 266
(CO)5 Mn Me 187
(CO)5 Re Me 220

The primary studies of Organometallic compounds were related with the


study of valency of metals. Because, these metals give only one organometallic
compound, compared to a series of oxides (due to variable valency). Further,
due to their volatility their purification is also easy, compared to inorganic
compounds. Organo metallic derivatives have in general been of greater interest
not only due to their fascinating structural and bonding variations, but also their
potential applicability.

1.3.1 Nomenclature
Based on Werner's and IUPAC rules of naming organometallic
compounds, names of Zn (C2 H5)2 will be diethyl zinc (II) and that of [Me3 Pt
Cl], Chloro trimethyl Platinum (IV), i.e. names of metal-alkyls and metal-aryls

6
may be derieved after naming the ligands in alphabatic order, name of the metal
follows with oxidation state in paranthesis.

1.3.2 Classification and Types


Organotransition metal compounds show wide variety. Some are quite
stable, while others are quite reactive. Some are ionic, and some are completely
covalent. On the basis of nature, bonding and structure organotransition metal
compounds are classified in to following three groups :
(a) Ionic
(b)   bonded covalent and
(c)  - bonded covalent compounds
Actual ionic Organometallic compounds are formed by strongly
electropositive s-block metals. Although, alkyl and aryl compounds of Mn, Zn
and Eu also show sufficient ionic property. In these compounds, hydrocarbon
radical is present in the form of carbo-anion and is bond with non directional
and electrostatic forces. These compounds resemble with alkali and alkaline
earth halide and hydrides.

For convenience, transition metal organometallics can be devided into


two broad groups:

(a)   bonded organometallics (   hydrocarbyls) in which a single


carbon atom of the ligand is attracted directly to the metal through   bond,
and (ii)   bonded organometallics, which are formed between a metal atom
and ligands such as CO, RNC, : CRR1, CR, RC  CR and other unsaturated
ligands.

7
Stable   bonded covalent organometallic compounds are generally
formed by metals having 18 electrons or nearly 18 electrons – subshell (d-block
metals of group 11 and 12, and p-block metals of group 13 to 16), while
  bonded organometallics of transition metals of with incomplete d-orbitals
are generally unstable.

 - bonded covalent organometallics are given by transition metals with


unsaturated subshells with hydrocarbon radicals.

Types of Organo Transition Metal Alkyls and Aryls

Alkyl and aryl derivatives of transition metal are   bonded


organometallics. In these compounds metal atom and alkyl or aryl radical share
one electron each to give 2 electron-2 centered M-C single bond. In this way
these alkyl or aryl radicals are monhapto (n 1) ligands, i.e. they are one electron
donors. Hapticity indicates the number of carbon atoms of the organic moiety,
which are within the bonding distance of the metal. Organotransition metal
alkyls and aryls are classified on different basis :

(a) On the basis of types of ligands present these are classified as


homoleptic or heteroleptic metal hydrocarbyls.

Homoleptic, MRn, are those metal hydrocarbyls in which all the organic
groups on the metal atom are the same e.g. Ti Me4, [Ti {CH (SiMe3)2}3]
and [V Ph6] etc.

While, heteroleptic, MR n-a Xa are those metal hydrocarbyls in which the


groups attached to the central metal atom are of more than one type e.g.
Ti Me 4-x [ L x], Zr Me2 (n5 C5 H5)2 and Zr Men (O Ph) 4-x etc.

8
(b) On the basis of nature of ligands, these are classified into 'Alkyl
Organometallics' or 'Aryl Organometallics'. Organometallics with alkyl
radicals are called metal alkyls, eg. Ti (Me)4, Hf (CH2 But)4, WMe6 etc.
Similarly, organometallics with aryl radicals are designated as metalaryls,
e.g. (Sc (Ph)3, [La Ph4]-, [V (Ph)6]4-, Hf (CH2 Ph)4 etc.

These compounds may be (i) Symmetrical, Zr Me4 or (ii) unsymmetrical,


Ti (Me)3 (Bu) or (iii) Mixed (Alkyl- aryl hetro-ligand) W Me2 (CH2 Ph)4
(c) On the basis of number of metal atoms, these are classified as mono
nuclear or polynuclear alkyl ( or aryl) organometallics. In polynuclear
organometallics metal atoms are linked to gether (i) through bridging
alkyl or aryl or (ii) directly of these with single or multiple bonds; in
some of these (iii) in addition to metal-metal bonding bridging alkyl or
aryl are also present (Fig. 1.1).

1.3.3 Routs of Synthesis


As has been shown earlier, for a long time it was considered that
alkyl and aryl derivatives of transition metals are highly unstable,
compared to their main group metal analogues, hence their preparation
was a difficult task. Latter it was known that the difficulty is not with the
thermodynamic aspect, but is due to Rinetic one (Table 1.1); as the metal
alkyls (or aryls) have tendency to decompose through many suitable
pathways and the most important one in these is   hydrogen
elimination. Thus during slat two decades, large number of alkyls of

9
Fig. 1.1 : Bi-and Poly nuclear Hydrocarbyls
various transition metals have been synthesised using the alkyl radicals
having no   hydrogen (eg. Ph CH2 CH3, CH3 C (CH3)3 etc.). The most
important example of this method is the synthesis of metal methyls, M
(CH3)n of different metals. On the same basis stability of metal benzyls
[M (CH2 C6 H5)n ] and metal neopentyls. [M (CH2 C6H5)3]n] may be
explained.

The influence of steric hindrance in inhibiting the approach of


  hydrogen in crowded tert butyl/isopropyl groups to the central metal

atom explains the comparative stability of derivatives like Cr{C(CH3)3}4.

Another additional factor can be cited to contribute to the stability


of derivative like M (CH2SiMe3)n, which are distinctly more stable than

10
the analogous neopentyls M(CH2CMe3)n. This can be understood as the
substitution of   carbon atom in the ligand by silicon precludes the
possibility of   hydrogen elimination as the formation of C = si
analogue of the alkene is very unlikely. Some other examples of ligands
of this type can be cited as –CH2GeR3 and –CH2SnR3 as well as
1-norbornyl in which case also the resulting bridge head alkene is highly
unstable). the cause of high stability is the fact that silicon, germanium
and tin have no tendency for formation of hydroalkene.

It may be pointed out that the decomposition of metal alkyls


through   hydrogen pathway involves the formation of intermediate
hydridoalkene complex

H....M
H
R' - C = C
H
R"
in which the coordination number of the metal has been increased. It,
therefore, follows that if the coordination sites of the metal were already
saturated by the presence of other ligands on the metal, then the
formation of the complex (B) would be precluded. A few examples of
derivatives of this type stabilized by the presence of the other ligands are
: Mo (CH2 CH3)(CO)3(  5-X5H5); Mn(CH2CH3) (CO)5: and Fe (  5-X5H5)
(CO)2(  5-X5H5). Such stabilizing ligands are generally   bonding or
  acid type, but could also be other Lewis bases like ammonia in [Rh

11
(C2H5)(NH3)5]CIO4)2 or bissalicylaldehyde-ethylenediimine (salen) in
(Co(C2H5) salen)].

Thus for making synthesis of transition metal alkyls and aryl


possible by stabilizing them, the following measures are taken :

1. Use of alkyl (or aryl) radicals with no  -hydrogen.

2. Use of radicals like t-butyl or isopropyl having crowded  -hydrogen


atoms (in which reach of metal atom is difficult to  -hydrogen).

3. In place of  -carbon, use of radicals, with silicon, germanium and tin


atoms (in which no tendency of hydrogen elimination is present).

4. Use of stabilizing ligands

Using these measures, now we have methods of synthesising alkyls (or


aryls) of almost all transition metals. Out of these methods, some are so
noble that there are no analogous methods available for the synthesis of
main group alkyls (or aryls). Amongst these methods most important is
halide carbanion exchange method, which is used for the synthesis of
alkyls (or aryls) of almost all transition metals.

Followed with is given methods of synthesis of alkyls (or aryls) of


transition metals of different groups of the periodic table. Here, it will be
interesting to note for metals of group VIII (Group 8, 9 and 10 of long
form Periodic table), large number of methods are used for synthesis of
their compounds.

1.3.3.1Hydrocarbyls of group 3 (d' metals)

In this group Sc, Y, Lanthanides and actinides elements are present.


These elements generally form mononuclear hydrocarbyls (some metal

12
form polynuclear one also) in their 3, 4, 6 and 8 oxidation states. (Table
1.2). The general methods used for their synthesis are (i) halide exchange
and (2) ylide synthesis :

Table 1.2 : Representative   hydrocarbyls of group-3 metals


Metal Oxidatio Coordination Alkyl (or Aryl) compounds
n State Number
(Hybridisation)
Sc +3 3(sp2) Sc (CH2 Si Me3)3 (thf)x'
Sc [CH (Si Me3)2]3'
Sc (Ph)3
y +3 3 (sp2) Y (CH2 Si Me3)3 (thf)x'
Y (CH (Si Me3)2]3
Y (Ph)3
4 (sp3) [Y (But)4]
[CP2Y  CH3)2 YCP2]
Lanthanides +3 3 (sp2) M (CH2 Si Me3)3 (thf)x'
(M = Tb, Er, Tm Lu; x = 0, 2 or
3)
[M (CH2 P Me3)3]+3, M =
Lanthanide metal
4 (sp3) [M Cl {CH (Si Me3)2}3}-,
(M = Tb, Er, Tm or Yb)
[M But4]-,
(M = Sm, Er, Yb or Lu)
[Lu (C6 H3 Me2)4]-
[M (CH2 Si Me3)4]-, [M Ph4]-
(M = Tb, Er, Tm, Yb)

13
6 (d2 sp3) [M Me6]3-,
M (-CH2)2 P Me2)3
(M – Lanthanide metal)
Actinides +4 4 (sp3) Th (CH2 Ph)4
6 (2 sp3) [U Me6]2-
[U (CH2 Si Me3)6 ]2-,
[U (Ph)6]2.
+5 8 Cubic [U (CH2 Si Me3)3]3.

1. Halide- Carbanion Exchange : Substitution of halide ion from metal


halides by Carbanion ion :
(i) M Cl3 + 3 Li CH2 Si Me3 THF

 [M (CH2 Si Me3)3] (thf)x + 3 Li Cl

(M = Sc, Y, Tb, Er, Tm, Yb, Lu. x = 0, 2, or 3)


(ii) M Cl3 + Li CH (Si Me3)2  [M {CH (Si Me3)2}3] + 3 Li Cl
(iii) M Cl3 + 3 Li CH (Si Me3)  [Li (thf)4]+[M Cl{CH (Si Me3)2}3]- + 2 Li Cl
(M = Tb, Er, Tm or Yb)
(iv) MCl3+4 Li But  t -
 [Li (thf4)+[M Bu 4)] + 3 LiCl
THF

(M = Y, Sm, Er, Yb or Lu)


(v) M Cl3 + Li C6 H3 Me2 -2, 6  [Li (thf)4]+ [M (C6 H3 Me2)4]4- + Li Cl
(M = Lu, Yb)
3
(vi) MCl2  6LiMe  3TMEDA  [MMe6 ]3 [Li(TMEDA)]3
Et 2 O
 3LiCl

(M = Lanthanide metal
(vii) UCl4 = 6Li Me  
Solvent
Li2 [U Me6]. 8 Et2 O/THF
( Et 2 O / THF )

6 Li Ph   Li2U .Ph6 ].8Et 2O / THF


Solent

6 Li CH2 Si Me3   Li2 [U (CH2 Si Me3)6]. 8 Et O/THF


Solvent

14
THF

(viii) ThCl4 + 4 Li CH2 Ph Th (CH2 Ph)4 + 4 Li Cl
LowTemp.

2. Ylide Synthesis
As has been shown, chelating ligands play important part in stabilization
of transition metal- alkyl bond. An important example of this is the use of
phosphorous ylide :

M = Lanthanide metal
1.3.3.2 Hydrocarbyls of Group-4 (d2 metals)
d2 – metals of group-4 in their +2, +3 and +4 oxidation states form
hydrocarbyls with coordination numbers 2, 3, 4, 5 and 6. Using the
ligands fulfilling stereochemical requirements, we generally get tri
coordinated alkyls (or aryls) which are stable at sufficient temperatures
(Table 1.3). Where as, Ti (iii) gives homoleptic compounds, Zr and Hf
form heteroleptic compounds. The methods used for synthesis of these
alkyls (or aryls) are (1) Halide exchange, (2) Transmetallation (3) Metal
hydride alkene insertion and (4) ylide synthesis :
Table 1.3 : Representative alkyls (or aryls) of group 4 Transition metals.

Metal Oxidatio Coordination Alkyl (or Aryl) compounds


n State Number
(Hybridisation)
Ti +2 2 (sp2) Ti (CH2 Ph) 2'
Ti Ph2

15
+3 3 (sp3) Ti (CH2 Si Me3)3;
Ti [CH (Si Me3)2]3;
Ti R (  5 C5 H5)2'
(R = P, 2, 6 Me2 C6 H3; 2, 4, 6-
Me3 C6 H2 etc.)
+4 4 (dsp2) Ti Me2 (DMPE)2;
4 (sp3) Ti Me4; Ti Ph4
Ti (CH2 But)3
Ti (CH2 Si Me3) 4;
Ti Me3 (5  C 5 H5)
Ti Me3 Cl, Ti me Cl3
+3 5 (dsp3) Ti Cl2 R (Py)2
(R = Me, Ph.)
+4 5(dsp3) [Ti Me]5-
Zr +4 4 (sp3) Zr Me4, Zr Ph4;
Zr (C6 H5)4;
Zr (CH2 Ph)4;
Zr (CH2 But)4;
Zr (Ch2 (Si Me3)4;
Zr Cl {CH (Si Me3)2}3;
Zr Cl (Ph) (  5-C5 H5)2
Hf +4 6 (d2 sp3) [Zr Me6]2-
+4 4 (sp3) Hf (CH2 But)4;
Hf (CH2 Ph)4;
Hf (CH2 Si Me3)4;
Hf Cl [CH (Si Me3)2]3

16
(1) Halide Exchange
(i) M Cl4 + 4 Li Me  
ROR
M (Me4) + 4 Li Cl
.80

(M = Ti Or Zr)
ROR
(ii) M Cl4 + 4 Mg (CH2 Ph) x M (CH 2 Ph) 4  4MgClx
 60C
(M = Ti, Zr Or Hf)
(iii) M Cl4 + 4 Li CH2 Si Me3  M((CH 2 SiMe 3 ) 4  4LiCl
Et o 2

(M = Ti Zr Or Hf)

Ti Cl3 + Mg (R) Br  Ti Cl2 (R) (Py)2 + Mg (Br) Cl


Py
(iv)
.30º C
(R = Me, Ph)

Ti Cl3(  5 – C5 h5)+3 Li Me 


ROR
(v) Ti Me3 (  5-C5 H5)2+ 3 Li Cl.
.30º C

2 Ti Cl (  5-C5 H5)2+2 Mg (R) x   


Pen tan e
(vi) 2 Ti (R) (  5- C5 H5)2 + 2
70º C
Mg Cl. x (R = Ph, C6 H3. 2, 6-Me2; 2, 4, 6-Me3 C6 H2)
1
(vii) Ti Cl4 +4 Li CH (Si Me3)2  Ti CH (Si Me3)3+4Li Cl + (Me, Si)2 CH
2
(viii) M Cl4 + 4 Li CH (Si Me3)2  M Cl [CH (Si Me3)2]3 + 3 Li Cl + Li
CH (Si Me3)2
(ix) Ti Cl2 (dmpe)2 + 2 Li Me ROR
 Trans Ti Me2 (dmpe)2 + 2 Li Cl

(2) Trans Metallation


Opposite to halide exchange reactions, these reactions give heteroleptic
alkyls (or aryls) :
2 Ti Cl4 + Zn Me2  2 Ti Cl3 Me + Zn Cl2
Ti Cl4 + Al Me3  Ti Cl3 Me + Al Me2 Cl

17
Ti Cl4 + Pb R4  Ti Cl3 R + Pb (R)3 Cl
(R = Me Or Et)
(3) Metal Hydride Alkene Insertion
Zr (H) Cl (  5 C5 H5)2 + Li Ph  Zr (Cl) (Ph) (  5 C5 H5)2 + Li H.
(4) Ylide Synthesis
Ti Cl4 + n Me3 P = CH2  Ti Cl4 (CH2 P Me3)n
(n = 2, 3)
Zr Cl4 + n Me3 P = CH2  Zr Cl4 (CH2 P Me3)n
(n = 2, 3)
M Cl2 (  5 C5 H5)2 =2 Me2 P=CH2  [M (CH2 P Me3)2 
5
C5 H5)2+ 2 Cl.

1.3.3.3 Hydrocarbyls of Group-5 Metals (d3 Metals)


d3- metals of group-5 form hydrocarbyls with coordination numbers 3, 4,
5 and 6 in their +2 to +5 oxidation states. These may be neutral or negative.
Ligands with no   hydrogen or with suitable stereochemistry form stable
alkyls (or aryls). However niobium and tantalum in their +5 oxidation state give
unusual results with Li CH2 Si Me3 ligand. (Table 1.4). The methods used for
the synthesis are : (1) Halide exchange and (2) Trans metallation :
Table 1.4 : Hydrocarbyls of d3- Metals
Metal Oxidation Coordination Alkyl (or Aryl) compounds
State Number
(Hybridisation)
V +2 4 (dsp2) VMe2 (dmpe) 2 Trans
+2 6 (d2sp3) [VPh6]4-
+3 3 (sp3) V(CH2 Si Me3)3;
V [CH (Si Me3)2]3;
V (2, 4,6-Me3C6H2)3

18
6 (d2sp3) V Ph3 (THF)3
+4 4 (dsp2) V Me4 VPH4,
V (CH2 SiMe3)4'
V (CH2 Ph)4;
Nb +4 4(sp3-) Nb (C6F5)4'
H
(Me3 (CH2)3 M= C
CMe3
+5 5(sp3-) Nb Me 5;
Nb Cl3, Me2;
Nb (CH2 SiMe2)2Cl3
6 (d2sp3) [Nb Ph6;]-
[Nb Me5 (dme) ]
Ta +5 5 (dsp3-) Ta Me5;
Ta (CH2 Ph)3'
Ta Cl2 Me3'
Ta Cl2 (CH2 SiMe3)3
6 (d2sp3) [Ta Ph6]-
Ta M5 (dme)

(1) Halide exchange


(i) VCl2 (dmpe)2 + Li me ROR
 V(Me)2 (dmpe)2 (Trans.) +2 LiCl

(ii) VCl3 (THF)3 + Li Ph  VPh3 (THF)3 + 3 Li Cl


(iii) VCl4 + 4 Li R  VR4 + 4 Li Cl
(R = Me, Ph)
(iv) VCl3 (NMe3)2+3 Li CH (SiMe3)2  V[CH(Si Me3)2]3+3 Li Cl+2NMe3

19
(v) VCl3 (THF)3+3 Mg X (2,4,6 – Me3 C6 H2) THF
 ,
 3Mg X Cl + V
30º C

(2,4,6 – Me3, 6H2)3


ROR


(vi) VCl4 + 4 Mg (CH2 Ph) x V (CH2Ph)4 + 4MgXCl
 60º C
(vii) VCl4 + 4 Li (CH2 SiMe3) ROR
 V (CH2 SiMe3)4 + 4LiCl

ROR


(viii) Nb Cl3 Me2 + 3 Li me + dMe Nb Me5 (dme) + 3 LiCl
 80º C
Et 2 O
(ix) Ta Cl2 Me3 + 2 Li Me TaMe5 dme

 TaMe5 (dme)
 78º c
H
(x) MCl- (CH2 CMe3)3 + 2 Li CH2 CMe3 Pentone
 (Me3 CCH2)2M= C
CMe3
+ 2 Li Cl + Me3 CCH3
(M = Nb or Ta)
(2) Trans Metallation
Weak alkylating agents react to give partial halide exchange resulting in
heteroleptic alkyls (or aryls) :
Nb Cl5 + ZnR2 Pen
tan
e  NbCl3 R 2  ZnCl2

2TaCl 5  3ZnR 2   2TaCl 2 R 3  3ZnCl2


Pen tan e

(R=Me, CH2, Si Me3)

1.3.3.4Hydrocarbyls of Group-6 (d4- Metals)


d4- metals of group-6 in their +2, +3, +4, and +6 oxidation states form
hydrocarbyls, generally with coordination numbers 3, 4 and 6. The elements of this
group have tendency to form binuclear alkyls (or aryls). However tungsten in its 8.
coordination number also form negative compounds (Table 1.5). These compounds
may be neutral or anionic. These alkyls are prepared by (1) Halide exchange method,
(2) Transmetallation (3) Ylide synthesis. Aryls of molybedenum can also be prepared
by the action of organic halides with anionic metal complexes :

20
Table 1.5 : Hydrocarbyls of Group -6
Metal Oxidation Coordination Alkyl (or Aryl) compounds
State Number
(Hybridisation)
Cr +2 2 (dsp2) Trans - CrMe2 (dmpe)2
[Cr Me4]2-
6 (d2sp3) Cr2 Me8]4-
+3 3 (sp2) Cr (CH2Ph)3'
Cr [CH (SiMe3)2]3
4(sp3) [Cr Ph4].'
[Cr (CH2 (Si Me3)4]
[Cr2 (CH2 SiMe3)4 (PMe3)2]
6 (d2sp3) Cr RCl2 (THF)3
(R = Me, Et, Pr, But)
Cr Ph3 (THF)3,
Cr [(CH2)2 PMe2]3 t
+4 4 (sp3) Cr Me4 ; Cr Bu+4;
Cr Pr4 ; Cr (CH2 SiMe3)4;
Cr R4 (R=CH2 CMe3
CH2C(Ph) Me2, CH2 CPh3)
6 (d2sp3) [Cr Me6]2-
Mo +2 5 (d2sp3) Mo (CH2Ph) (CO)3 (  ' C5H5)
+3 6 (d2sp3) (Mo2 MeM)4-
+4 4 (sp3) Mo (CH2 Ph)4; Mo (Mes)4
Mesitylene
+5 6 (d2sp3) Mo2 R6
(R=CH2 Si Me3, CH2 C Me3)

21
W +3 6 (d2sp3) W2 Me82-
+4 4 (sp3) W (CH2Ph)4;
6 (d2sp3) W Ph62-
+5 5 (d2sp3) W (Ph)5
+6 6 (d2sp3) W Me6 ; W (R) Cl3
(R = Me, Ph, Et, But)

(1) Halide Exchange


(i) CrCl2 (dmpe)2 + 2 Li Me ROR
 Trans Cr Me2 (dmpe)2 + 2 Li Cl

(ii) CrCl3 + 3 Li CH (Si Me3)2  Cr {CH (Si Me3)2}3 + 3LiCl



(iii) CrCl3 (THF)3 + 4 LiR  Li CrR4  CrR4
Dioxane
(iv) CrCl3 + 6 Li Me Li3 [Cr Me6]3 + 3 Diox. + 3LiCl
 18º c
(R= CH2SiMe3, CH2CMe3, CH2C(Ph)Me2, CH2CPh3 or But)
(v) MoCl3 (THF)3 + 5 Li Me THF
 Li4 [Mo2 Me8] [THF)4

(vi) MoCl5+MgCl(CH2 Si Me3)  MO2(CH2SiMe3)6 or Mo2 (CH2 CMe3)6


(vii) W Cl6 + 6ALMe3  W Me6 + 6 Al ClMe2
(viii) W Cl6 + MgCl (CH2 Si Me3)  W2 (CH2 Si Me3)6 or Li CH2 SiMe3
(ix) WCl4 (O) + C6H4 (CH2MgCl2) THF
 W (CH2C6H4CH2-O) +3 MgCl2

(2) Trans Metallation


(i) CrCl3(THF)3+AlR3 THF

 CrRCl2 (THF)3 Or Al R2 (OEt) or Al R2 (OEt)

(R = me, Et, Pr or But)


(ii) W Cl6 + MR  W Cl5 R
(MR = Hg Me2 (Ether), R = Me
= Zn Me2(CH2 Cl2 in ether)R = Me
= Zn Ph2 (in Ether) R = Ph
= Sn Me4 (in Hexane) R = Me

22
= Sn Et4 ((") R = Et
= Sn Bu4 ( ") R = Bu
= Sn Ph4 (") R = Ph.

(3) Reaction of Anionic Metal Complexes with Organic Halides


For this generally sodium salt of carbonilate is used, e.g. in the synthesis of
molybdenum hydrocarbyl :
Na [Mo (CO)3  5 -C6H5) + Ph CH2 Cl  Mo (CH2 Ph) (CO)3 (  5 -C5H5) + NaCl
(4) Ylide synthesis
(i) Cr (CO)5 (PPh3) + Ph3P = CH2  Cr (CH2 PPh3) (CO)5 + PPh3
CH2
(ii) Cr Cl3 (THF)3 + 3 Li (CH2)2 PMe2  Cr PMe2 +3LiCl
CH2
3

(iii) Li4 [Mo2 Me8] + 4 Me4 PCl  [Mo2 {(CH2)PMe2}4] + 4CH4 + 4 LiCl
(iv) react with metal chlorides to give spirocyclic derivatives : Ylide of
Phosphorous

1.3.3.5 Hydrocarbyls of Group 7 (d5 – Metals)


d5 metals of group 7, in their +1 to +6 oxidation states form hydrocarbyls
with 4 and 6 coordination numbers. These compounds have tendency to
polymerise and maximum number of compounds are obtained as dimer or
polymer (Table 1.6) These are synthesised by (1) Halide exchange (2)
Reactions of anionic metal complexes with organic halides (3) Insertion of
unsaturated compounds in M-C bond and (4) Elimination of CO from acyl-
compounds :

23
Table 1.6 : Hydrocarbyls of Group-7
Metal Oxidatio Coordination Alkyl (or Aryl)
n State Number
Mn +1 6 (d2sp3) Mn (CF3) (CO)5;
Mn (CH3) (CO)5;
Mn [C(:O) CH3] (CO)5;
Mn [C (:O) Ph] (CO)4; (PPh3)
Mn [C6H4 Me] (CO)5
+2 4 (sp3) Mn Me2 (dmpe)2 ;
Mn Me42-, Mn (CH2 SiMe3)42-
[Mn{CH2C(Ph)Me2}2]2;
[Mn {CH2CMe3}2]2;
[Mn {CH2 Si Me3}2]2
+3 4 (sp3) [Mn (CH2CMe2PPh3)3]2
+4 4 (sp3) [Mn (CH2But)2]4
[Mn (CH2Si Me3) 2] n;
[Mn{C(Si Me3)3]2
Re +3 4 (sp3) Re2 (  Si Me3) 2 (CH2 Si Me3) 4
6 (d2sp3) Re2 Me82-
+4 6 (d2sp3) Re3 (CH2 Si Me3 ) 12
+6 6 (d2sp3) Re Me6

(1) Halide Exchange


(i) MnCl2 + 4LiMe ROR
 Li2 [Mn Me4] + 2LiCl

(ii) MnCl2 + MgMe depe


 Trans Mn Me2 (dmpe)2 + 2LiCl

(iii) MnCl2 + 4LiCH2 Si Me3  Li2 [Mn (CH2 Si Me3)4] + 2 LiCl


(iv) MnCl2+2MgCl(CH2C(Ph)Me) ROR
 [Mn{CH2 C(Ph) Me2}2] 2 + 2MgCl2

24
(v) MnCl2 +2 MgCl (CH5CMe3) ROR
 [Mn (CH2CMe3)2]2 + 2MgCl2

or Mg (CH2 Si Me3) ROR


 Mn (CH2 Si Me3)2]4+ 2MgCl2

(vi) ReOCl4+ LiR  ReOMe4 AlMe


  ReMe6

or 4 MgRx
TMEDA  +2Lime
[Re2 Me8]
(vii) ReCl4 +(THF)2+MgCl(CH2 SiMe3) 
N
Re2(  -CSiMe3)2(CH2SiMe3)4
2

+N2 {Re(CH2 Si Me3 ) 4 }2]


(viii) Re Cl4 (THF)4 + MgR2  Re3 R12
(2) Reaction of Anionic Metal Complexes with Organic Halides
(i) Na [Mn (CO)5 ] + CH3 I  Mn CH3 (CO)5 + Nal
(ii) Na (Mn (CO)5]+ CF3COCl  Mn (COCF3) (CO)5 + NaCl
(3) Insertion of Unsaturated Molecules in M-C Bond
(i) Mn Ph (CO) 5 + PPh3  Mn {Mn (CO)Ph} (CO) 4 (PPh3)
(ii) Mn CH3 (CO) 5 + CO  Mn (CO) CH3 } (CO) 5
(4) Elimination of CO from Acyls
Mn (COC6 H4 Me) (CO) 5 Energy
 Mn (C6 H4 Me) (CO) 5 + CO

1.3.3.6 Hydrocarbyls of Groups 8, 9, 10 Metals


d6, d7 and d8 metals of groups 8, 9 and 10 respectively in their +2 to +4
oxidation states form many hydrocarbyls with coordination numbers 2, 3,
4 and 6. These compounds may be positive, negative or neutral. Various
methods are used for their synthesis. Important methods out of these are :
(1) Halide exchange (2) Transmetallation, (3) reaction of anionic metal
complexes with organic halides (4) Insertion (5) Oxidative addition (6)
Cyclic Metallation (7) Elimination (8) Ylide synthesis etc. :

25
Table 1.8 : Representative Hydrocarbyls of Group 6, 7 and 8 Metals
Metal Oxidation Coordination Alkyl (or Aryl)
State Number
Fe +2 2 (sp) Fe (Mes)2 Mesitylene.
+2 4 (sp3) Fe {CH (CH3) (CN)} (CO)2  5C5H5),
Fe Ph (Co)2 (  1C5H5),
FeR(Co)2 (  1 C5H5)
Fe Me2 (dmpe)2
Co +1 5 (dsp3) Co (CF2 CF2H) (CO) 4
+2 4 (sp3) Co Ph2 (dipy);
[C0Me4]2-
+3 3 (sp2) [Co Ph2 (  6C6H4 Me)]
+3 6 (d2sp3) CO (C=CR)63-
+4 4 (sp3) CO R4
6 (d2sp3) [C0(CH2Ph) (CN) 5]2-
Ni +2 2 (sp) Ni Bu2; Ni (Mes)2
+2 4 (sp3) Ni (CH2 Si Me3)2 (bipy)
Ni Et2 (biby);
Ni Me42-; Ni Ph42-
Ni Ph2 (dipy)
+3 3 (sp2) Ni Ph2 (  6-C6H4Me)
6 (d2sp3) [Ni (CH2 Ph) (CN) 5]2-
Ru +2 6 (d2sp3) Ru(CH3) (I) (CO)2 (PPh3) 2
Rh +3 3 (sp2) Rh (Mes)3
6 (d2sp3) [Rh (Et) (NH3) 5 ]2+
Pd +2 4 (sp3) [Pd (>CH2 S Ph) 2] 4
Ir +3 6 (d2sp3) Ir Me (CI)(I)(CO)(PPh3)2

26
Ir Cl2 (C6H4Me)(CO)(PPh3)2
Pt +2 4 (dsp2) Pt Me2 (PPh3)2
Pt Me (O2C CF3)(PPh3)2;
trans Pt Cl (Ph)(PPh3)2;
Pt (C  CR)Cl(PPh3)2

(1) Halide Exchange


(i) Fe Cl2 (dmpe)2 +2 Li Me ROR
 Fe Me2 (dmpe)2 + 2LiCl

Fe Cl3 (OEt2) + 4 Li Me 


ROR
(ii) Li2 [Fe Me4] + 3 Li Cl
 20º C
(iii) Ni Cl2 (PEt3)2 + 2Mg Br (Mes)  Ni (Mes)2 (PEt3)2 + 2 MgBrCl
Vacuum 
Ni (Mes)2 + 2 PEt3
(iv) Ni(  3-C3H5)2Br+4Mg Br(Mes)  2Ni (Mes)2+ 2MgBr2 + 2Mg (C3H5)Br
(v) Ni Cl2 (Py)2 + 2Mg (CH2 Si Me3)Cl  Ni (CH2 Si Me3)2 (Py)2+2 MgCl2
(vi) Rh Cl3 (SC4H6) + 3Mg (Mes)Br  Rh (Mes)3 + SC4 H6 + 2 Mg BrCl
(vii) Pd Cl2 (L)2 + 2 Li Ph  Pd Ph2 (L)2 + 2 Li Cl; (L – Bidentate)
(viii) Pd Cl2 (PhCN)2 + 2Li CH2 S Ph  (Pd (CH2S Ph)2}4 + 2 LiCl + 2 Ph CN
(ix) Pt Cl3 (PEt3)2 + 2 Li Me  Pt Me2 (PEt3)2 + 2 Li Cl
CuI
(x) Pt (PR3)2 Cl2+R'C  CH+NEt3  trans Pt (C  CR) (Cl) (PR3)2 +HI
 CuCl
(2) Trans metallation [Alkylation of Pt –C [Bond]
(i) Pt Cl2 (PR3)2+ Hg Ph2 EtoH
 trans Pt (Ph) Cl (PR3)2 + Hg (Ph)Cl
C 2 H 2 Cl 4
(ii) Pt Cl2 (1, 5-Cod)+Sn Me4 Pt Me2 Cl (1,5-Cod)+Sn Cl Me3
100º C
(iii) Pt (O2CCF3)2 (PMe2Ph)2 + Sn Me4  trans Pt Me (O2 CCF3) (PMe2 Ph)2

27
(3) Reaction of Anionic metal Complexe with organic Halides
(i) Na [Fe (CO)2 (  5-C5H5)+ C6 F6  [Fe (Ph) (CO)2 (  5–C5H5) +Na F
(ii) Na3 [CO (CN)5] + Ph CH2 Br  Na2 [Co (CH2 Ph) (CN)5] + Na Br
(iii) Na [Co(CO)4+CH2=CH2 Br  Co (CH2-CH=CH2) (CO)4 + NaBr

Co (CO)3 (  3-C3H5)+CO
(4) Insertion Reactions
(i) Insertion of Multiple Bonded molecule in M-H Bond
FeH (CO)2 (n5 C5H5) + CH2 = CHCN  Fe {CH (CH3) CN} (CO)2
(  5 – C5H5)
Co H (CO)4 + C2 Fe4  Co (CF2 CF2 H) (CO)4
[RhH (NH3)5]2++ C2H4  [Rh (C2H5) (NH3)5]2+
(ii) Insertion of Unsaturated molecules in Metal-Metal Bond
Co2 (CO)8 + C2F4  (CO)4 Co-CF2CF2-Co (CO)4
(iii) Insertion of Unsaturated Molecule in MC Bond
Trans Pt Cl (CH3) (PEt3)2 + CO  Trans Pt (C:O) Ph (CO)4 (PPh3)
(5) Elimination Reactions
(i) Elimination of CO from Acyl Compound
Li [Co(CO)4] + F3C COCl  Co (CO CF3) (CO)4 + LiCl

CO (CF3)CO)4+CO
(ii) Elimination CO2 from Carboxylates
Ni (CO2Ph)2 (biby) Heat

 Ni Ph2 (biby) + CO2

K2 Pt Cl4 + 2 TlO2 C Ph + 2Py 


Trans Pt (Ph)2 (Py)2+2KCl+2TlCl+CO3
(iii) Elimination of SO2 from Sulphonate
Fe (SO2R) (CO)2  5-C5H5 Heat

5
 FeR (CO)2  -C5H5 + SO2

28
[Pt (SO2Ph) Cl (PR3)2 Heat

 PtCl (Ph) (PR3) + SO2]
IrCl2 (SO2C6H4Me) (CO) (PR3)2 Heat


IrCl2 (C6H4Me) (CO) (PR3)2 + SO2


(6) Cyclometallation Alkyl (Acyl) groups linked with N or P coordinated
ligands show oxidative addition which involve breaking of sp3-
hybridised C-H bond and formation of M-C bond :
(i) FeCl2 (PMe3)3 + PMe3   [FeH{CH2PMe2}(PMe3)4]+2NaCl
Na / Hg

(ii) Chatt and Devidson (1965) process -

(7) Metal-Atom Reactions : Oxidative Reaction of Co condensation of


Organic Halides with Metal Vapours :
-
(i) M + 2 C6H5 Br 
196º C
 MBr2 + M (C6 H5)2 (  6 C6 H4
 M (C6H5)2 PhMe
Me) (M = Co or Ni)
(ii) Use of Reactive Metal Powder (Fe, Co, Ni, Pd Or Pt) give many
Hydrocarbyls :
2M + 2 C6 H5 X + 2 Et3  M (C6H5)2 (PEt3)2 + M X2
(iii) Pd + C6H3I + bipy  Pd (C6H5) (Bipy)
(8) Nucleophilic Reaction of Metal-Alkene : Alkene complexes of
transition Metals with Nucleophilic Radicals :
(i) [Fe(CO)2(  5-C5H5)(  2-C2H4)++PPh3  [Fe(CH2CH2PPh3)(CO)2  5-C5H5)]

(ii) [Rh Cl Et (  5-C5H5) (  2-C2H4)+ 


R
[Rh (Bu) Cl (R)(  5-C5H5)]

29
(iii) [Pd(PPh3)(  5-C5H5)(  2-C2H4)+ 
R
[Rh(Bu) Cl (R)(  5- C5H5)]
(iv) Cis [Pt Cl2 (Py) (  2-C2H4)] + Py  Cis [Pt Cl2 (CH2CH2Py) (Py)]
1.3.37 Hydrocarbyls of Group 11 (d9 – metals)
d9- metals of group-11 in their + 1 to +3 oxidation states give
hydrocarbyls with coordination numbers 1 to 3. Maximum number of
these alkyls (or aryls) have tendency to polymerise (Generally tetramer
formation). The general method of their synthesis is halide exchange
reaction (Table 1.9) However some hydrocarbyls of silver are prepared
by ylide synthesis :
Table 1.9 : Representative Hydrocarbyls of Group-11
Metal Oxidation Coordination Alkyl (or Aryls)
State Number
(Hybridisation)
Cu +1 1 [Cu (C6F5)]4
[Cu (CH2 Si Me3)]4
[Cu R]4 (R=Ph, Me2 C6H3)
+1 2 (sp) Cu (Me5)2; Cu (C  CR)2,
Cu Me2-; Cu (CH2CH2 PMe3)-2
+2 2 (sp) Cu R2 (R=CH2CH2PMe3)
+2 3 (sp2) Cu (Mes)-
Ag -1 1 [Ag Mes)]5,
+1 2 (sp) [Ag {C (SiMe3)3}2],
Ag (C  CR)2-
Au +1 1 [Au (Mes]5; Au (C  CR)
+1 2 (sp) Au Me2; Au (C  CR)2
+2 2 (sp) Au (CH (Si Me)2 ] (L)
2
+3 3(sp ) [Au Ph3]
+3 4 3 (sp3 [Au Me4]

30
(1) Halide Exchange :

2 CuCl + ZnR2 


ROR
(i) 2 (CuR]n + ZnCl2
10º C
(ii) CuCl + 2 Li Me ROR
 Li (Cu Me2) + Li Cl

(iii) 4 Cul + 4 Li (CH2 Si Me3)  [Cu (CH2 Si Me3)]4 + 4 Li I


(iv) MI – [Li (thf)4]+ [Li R2]-  [Li (thf)4]+ [MR2]- + Li I
(M=Cu, Ag) R = C(SiMe3)3 )
(v) AuCl(L)+Mg RCl  AuR(L) + MgCl2 (R= (SiMe3)3; L =Me,Ph,PR)
(vi) Au Cl(CO) + 5Mg Br (Mes THF

 [Au (Mes)]5 + 5 Mg BrCl

(2) Ylide Synthesis :


CH2 Ag CH2
2 Ag++2 Me3P = =CH  Me2 P PMe2
CH2 Ag CH2

31
CHECK YOUR PROGRESS – 1
Notes : (1) Write your answers in the space given below.
(2) Compare your answers with those given at the end of this
unit.
(a) (i) Metal hydrocarbyls, the   bonded organometallics are
........... and ................... derivatives of metals e.g. Me 3 Pt Cl,
IUPAC name of which is ...................................
(ii) On the basis of types of ligands metal – hydrocarbyls are
classified into (1) ........................ (eg ........................ and
....................., general formula .............................................)
and (2) ....................................... (e.g....................................,
general formula .........................................)
(iii) The hapticity of ligand is related with the .........................
..................................................................................................
..................................................................................................
(b) (i) Transition metal hydrocarbyls have been considered
................................................... compared to their main
group analogues. Hence, their synthesis has been ...............
...................., while ............................... is mainly due to
............................ rather than thermodynamic factor.
(iii) The most important path of their decomposition is
.............................................................................................
(c) (i) An example of halide exchange reaction is (Equation only):
.............................................................................................
(ii) An example of transmetallation is (Equation only) :
.............................................................................................
(iii) An example of ylide synthesis is (Equation only) :
..............................................................................................
32
1.3.4: Stability of Transition Metal Hydrocarbyls
Compared to main group   hydrocarbyls the transition metal analogues
are generally much less stable, although the instability is mainly due to kinetic
rather than thermodynamic factors. In view of much greater diversity in their
nature, it is rather difficult to attempt a simple generalization of their properties,
but an attempt would be made to correlate some of these on the basis of their
coordinative unsaturation and steric congestion.
The M-C bond in transition metal hydrocarbyls is also as strong as it is in
case of main group metal hydrocarbyls. We know alkyl and aryl groups are one
electron, monohapto-ligands. Alkyl and aryl radicals resemble with hydrogen
and halogens in the presence of unpaired electron. Thus, just like H. or .X they
also combine with metal atom sharing their unpaired electron, to form metal
alkyl or metal aryl.
H, CH3,.C6H5 , .X (X = F, Cl, Br, I)
M.+ .H  MH Or M-H (Metal Hydride)
M. + .X  MX Or M-X (Metal Halide)
M.+ CH3  MCH3 Or M-CH3 (Metal Alkyl)
M. + C6H5  MC6H5 Or M-C6H5 (Metal Aryl)
The nature of the bond, on the basis of electronegativity of metal may
vary from purely ionic to purely covalent. In ionic alkyls and aryls of Mn, Zn
and Eu hydrocarbon radical is an anion (i.e. in the form of rarbanion ion), which
is formed as a result of transfer of electron from valency shell of strongly
electropositive metal to valency shel of carbon (making the unpaired electron
present in alkyl or aryl radical paired) :

33
Covalent or polar – covalent alkyl or aryl may be supposed to form as a
result of overlapping of metal orbital having unpaired electron with the valency
orbital of alkyl or aryl radical having unpaired electron :

Electronegativity of carbon is 2.5, hence in hydro-carbyls of transition


metals, carbon is always negative as compared to metal atom, and M-C bond is
polar. The polarity of M-C bond depends on the hydrocarbon radical also
attached to metal, in addition to electronegativity of metal atom. The
electronegativity of hydrocarbon radical attached to metal depends on the
presence or absence of hydrogen on the group. Presence of excess of hydrogen
on the group makes it rather more positive, while absence of hydrogen or
presence of F, Cl or O atom makes hydrocarbon radical more negative. This
also increases stability of M-C bond, e.g. in comparison to alkyl or aryl
compounds, fluoro alkyls or fluoroaryls have higher thermal stability.

For example, where as (CH3 Co(CO)5 is stable upto – 20ºC only, CF3 Co
(CO)5, 91ºC, 91ºC, distills without decomposition. Fluorine makes M-C bond
more polar by attracting electrons towards itself. Thus the bond energy has an

34
increased ionic contribution. Further on increase of positive charge on metal
atom, contracts d-orbitals, which decreasing the non bonding interaction,
increases better overlap between bonding metal d-orbitals and ligand orbitals.

During synthesis of transition metal hydrocarbyls one more phenomenon


takes place, that is the nature of alkyl (or aryl) carbon changes from
electrophilic to nucleophilic, i.e. with the increase in electroneutrality tendency,
increase in M  L back-bonding tendency is seen. That is, ability to form
  bonding increases. This increases stability of these compounds. We know,
presence of CO, CN, pyridene etc. ligands (which help M  L bonding in
transition metal alkyls or aryls, increases their stability : e.g. Mn (CH2CH3)
(CO)5, Mo (CH2CH3) (CO)3 (  5 C5 H5) etc. are quite stable.

One of the distinguishing characteristics of transition metal


  hydrocarbyls is their coordinative unsaturation, which leads to their
instability through facile decomposition paths. On the other hand, this
unsaturation also explains the tendency of these compounds to act as Lewis
acids with a variety of donor ligands; the presence of these ancillary ligands
confers a comparative stability on these derivatives, for examples: the addults,
TiMe4(biby):TaMe5(dme);CoMe(diphos)2(diphos=1, 2-bis (diphenylphosphino)
ethane); MMe2 (dmpe)2(M=Ti,V,Cr,Mn,andFe,dmpe=1,2-bis (dimethylphos-
phino) ethane), NiEt2(bipy); and Ln(CH3SiMe3)3 (thf)n (Ln = a lanthanide
metal, n = 2 or 3) are more stable than the uncoordinated   hydrocarbyls.
Chelating hydrocarbyls like C6H4CH2NMe2-0, 0CH2C6H4NMe2; etc.,
also tend to provide stability to   bonded derivatives by blocking the
available coordination sites e.g.

[Cr{CH2C6H4NMe2 -0}3] and [Co{C6H4CH2NMe2}3].

35
Another mode by which these derivatives tend to satisfy their
coordination environment is by forming polynuclear species through alkyl or
other bridging legands or through multiple metal-metal bonding. The
association through bridging would obviously be hindered by more ramified
ligands. thus resulting in mononuclear species. Formally these would be
coordinatively unsaturated yet they attain thermal stability probably due to
steric congestion of the ligands which inhibits approach of reactive species.
Thus one of the attractive areas of research since 1970s has been to prepare a
variety of sterically demanding ligands in an attempt to prepare transition metal
  hydrocarbyls in low coordination states, e.g., [Ti{CH(SiMe3)2}3],
[Cr{CH(SiMe3)2}3], Mn{C (SiMe3}2], etc.
For any particular metal, the coordinative unsaturation will increase with
lowering of the oxidation state of the metal and lead to greater associative
tendency. For example, compared to the monomeric character of Ti (C 6H5)4, the
polymeric nature of {Ti (C6H5)2]n can be cited.
Transition metal   hydrocarbyls may be of three types, i.e., neutral,
anionic, and cationic. The formation and stability of anionic species of the types
[Ti(C6H5)5] and [Zr(C6H5)6]2- can be understood as in these, the central metal
atoms are coordinatively less unsaturated than in the corresponding neutral
species. Ti(C6H5)4 and Zr (C6H5)4, respectively.
On the same grounds, one would not expect the cationic species to be
formed easily; in fact, these often require a chelating hydrocarbyl of the type
Me3 P=CH2 which for example confers stability on cationic species of the
types:

36
Generally, with the increase in atomic weight of a metal, the M-C bond
energy of transition metal hydrocarbyls gradually increases (Table 1.1) i.e. for
the same metal, 'E' values follow the order Ph > Me > Et. The interesting
observation of the higher value of 'E' for M-C (CH2SiMe3) compared to that for
M-C(CH2CMe3) bond could probably be ascribed to the greater steric effect of
the latter (neopentyl) group, which could possibly lead to lengthening of the M-
C bond.

1.3.5 Decomposition Pathways


As discussed earlier the comparative instability of transition metal
  hydrocarbyls is of kinetic origin and they are comparatively more labile due
to the coordinative unsaturation of the transition metals, leading to facile
pathways for their decomposition and reactivity. In simpler terms these
decomposition pathways may be classified in the following three types : (i)
migration of a substituent (generally hydrogen) from a   bonded hydrocarbyl
to the metal; (ii) intermolecular reductive elimination; or (iii) homolytic fission
of M-C bond.A brief description of these types is being presented below :
(i) Migration of a substituent from a   bonded hydrocarbyl to the metal
occurs more commonly from the   carbon atom (   elimination) and less
frequently from  -elimination). A third type, i.e.  - elimination, which has
been observed for some main group hydrocarbyls, does not have any
established example in transition metal chemistry.
(a)   Hydrogen elimination

Out of the several pathways by which transition metal alkyls can


decompose, one of the most facile routes preferred by them is through the so-

37
called hydride transfer accompanied with alkene-elimination. This type of
reaction involves the transfer of a hydrogen from the second or   carbon atom
of the alkyl chain to the metal, increasing its coordination number. The
resulting intermediate hydrido-alkene complex tends to lose alkene with the
formation of metal hydride which in some cases may decompose to metal and
hydrogen.

(b)   Elimination reactions : These are of considerable synthetic utility in


main group   hydrocarbyls and involve the transfer of a substituent 'R' from
the   carbon atom to the metal with elimination of a carbene which may
remain coordinated to the metal:
  Elimination pathway has been much less observed in transition metal

hydrocarbyls and the main examples involve metal methyls. The binary
permethyls such as TaMe5, WMe6, and ReMe6 are not very stable and tend to
decompose explosively with the formation of methane, e.g.,
WMe6  3CH4 + "W (CH2)3'
In view of the metal being in its highest oxidation state, an internal
oxidative addition of the type :
H

M  CH 3  M  CH 2

38
is not feasible for the above decompositions which could occur either via
homolytic fission (free radical mechanism) or   elimination through a four-
centre transition state :

This pathway plays a key-role in the synthesis of alkylidene complexes.


A number of metal benzyls and neopentyls such as those of titanium and
tantalum have been shown to decompose by this pathway. Another mechanism
of   elimination, which is recently (1982) recognized, involves agostic
hydrogens (C-H-M).
The term "agostic" is used particularly in those situations where a
hydrogen atom is covalently bonded both to a carbon atom and a transition
metal atom. Evidence for such interaction (C-H-M) has been studied
spectroscopically and is being illustrated below :

The role of spectroscopically recognized 'agostic' C-H interactions has


now been confirmed crystallographically by the near octahedral environment
around rhodium in the following derivatives.

39
It has also been shown by crystallographic analysis that when a methyl
group is attached to a dº metal centre which has a less than 18-electron
environment, the one of the C-H bond of the methyl group is distorted in such a
manner that it lies within the bonding distance of the metal:

Such strong interactions between metal and a C-H group have been
shown to play a key role in cyclometallation and alkene polymerization
reactions.
(ii) Intermolecular reductive elimination pathway is the reverse of
oxidative addition reactions and can be represented as :
X
LnM LnM + X - Y
Y
Both the oxidation state as well as the coordination number of the central
metal 'M' are reduced by two units and hence, this type of pathway would be
confined to metals with stable oxidation states differing by two units, which is
more common with later transition metals.

40
A few examples of this type of pathway are given below :
(a) AuMe(PPh3)  AuMe (PPh3) + C2H6
(b) Organometal hybrides often decompose by this route and such reactions
assume special significance in catalytic hydrogenation processes :
PtH(R)(PPh3)2  Pt (PPh3)2 + RH
(c) Reductive elimination frequently follows oxidative addition, and in many
important catalytic processes both these phenomena play a crucial role
An illustrative example of stoichiometric reaction is depicted below :
Au (CH2SiMe3) (PPh3) + MeI  AuIMe (CH2SiMe3)(PPh3)

Aul (PPh3) + SiEtMe3


(d) Alternatively complexes in which the orbital occupation is higher than
usual for the concerned metal will be more susceptible to undergo
elimination reactions, and any reaction or change in conditions which
increases orbital occupation is likely to be followed by a counter-
balancing elimination. such effects are most noticeable towards the end
of the transition series. In Such effects are most noticeable towards the
end of the transition series. In such cases the formal oxidation number is
less important than electron availability at the metal. These points may be
illustrated by the following example:
NiEt2 (biby)  Ni + bipy + C4H10
(iii) Homolytic fission of M-C bond appears to be a common pathway
for decomposition of main group alkyls is also seen with transition metal
alkyls.
Zr (CH2 Ph)4  Zr + 2Ph – CH2 CH2 Ph

41
1.3.6 Characteristic Reactions :
  Bonded transition metal organometallics exhibit great diversity in
their reactivity patterns, which obviously depend upon the nature of the
metal as well as on the other ligands present. The chemical reactions of
importance to our discussion fall into six main categories : (a) metal-
carbon bond cleavage reactions, (b) elimination of an alkene and proton
abstraction, (c) replacement of one hydrocarbyl ligand by another. (d)
adduct formation, (e) redistribution reaction. and (f) insertion reactions
into metal-carbon bond.

(a) Metal-Carbon Bond Cleavage


Transition metal alkyls are only weakly nucleophilic, hence, differing
from main group metal alkyls, decompose only in presence of proton :

(i) Ti Me4 – 4 Me COOH  Ti (O2 CMe)4 + 4CH4


ROR

(ii) Zr (CH2 Si Me3)4+4HOC6 H5 Pr2  Zr (2, 6Pr2 C6H3O)4 + 4 Si Me4

(iii) Cr Ph3 (THF)n + ACCH  Cr (Acac)3 +3 C6H6+ n THF

2HCl HCl


(iv) Cis[PtCl2(PEt3)2] CisPt Me2 (PEt3)2 Cis [Pt+Cl (Me)(PEt)2]
 
 2 CH4  CH 4

Nucleophilic reaction on alkyls in oxidative conditions will also


come in this category :

(v) Mn Me (CO)5 + Br2  Me Br + Mn Br (CO)5

(vi) Ti Me4 + 4I2  4 MeI + Ti I4

(vii) CoMe2 (PMe3)3 + X2  CoX (Me) (PMe3)3 + MeX

42
(b) Elimination of alkene with proton transfer (   Decomposition)

(i) Pt Cl (CH2 CH3) (PEt3)2  Pt H Cl (PEt3)2 + C2H4

(ii) Cu(CH2CH2CH2CH3)(PBun3)  C2H5 CH = CH2 +Cu H (PBun3)

(iii) Mn CH2 CH3 (CO)5 + Ph3 C+BF4  Ph3 CH + [(CO)5 Mn (C2H4)+


(BF4)

(c) Replacement reactions-

(i) [Pd Me2 (bipy] + 2 C3H7 I  [Pd (C3H7)2 (bipy)] +2 CH3 I

(ii) M (CH2Ph)4 + 2 EtOH  M (CH2 Ph)2 (OEt)2 + Ph.CH3

(M = Ti Or Zr)

(iii) Zr Me2 ( 5 C 5 H 5 ) 2 + MeOH  Zr Me (OMe) ( 5 C 5 H 5 ) 2 +CH4

(d) Adduct Formation : This reaction generally takes place in presence of


coordinating solvents or ligands, which help in coordination-saturation :

(i) [MnR2]n + TMEDA  MnR2 (TMEDA)

(R= CH2 CMe3, CH2 Si Me3 Or CH2 (Me2 Ph)

(ii) Ti Me2 – dmpe  Ti Me2 (dmpe)2

(iii) Ta Me5 + dme  Ta Me5 (dme)

(iv) [Mn (CH2 Si Me3)2]a+2 Li CH2 Si Me3  Li2 [Mn (CH2 Si Me3)4]

(e) Redistribution: reactions comparatively less seen in transition metal


alkyls:

(i) 2 Ni (R)x (PEt2)2  Ni R2 (PEt3)2 + Ni R2 (pEt3)2

(ii) Cis=Pt Me2 (PEt3)2+Cis Pt Cl (PEt3)2  2 Cis Pt Cl (Me) (PEt3)2

(f) Insertion Reactions : Unsaturated ligands CO, CO2, CNS, SO2 etc. show
insertion in to M-C bond to give new products:

43
(i) CO insertion :

(ii) CO2 SO2 or CS2 inertion :


Cu Me (PPh2) CO
 Cu (OC Me) (PPh3)3
2

O
Cu Me (Et2O) (PPh3)2 CO
 2

 Au (n1 – SO2 Me) (PMe3)


Au Me (PMe3) SO
 2

Au Me3 (PMe3) SO



 Cis-Au Me2 (SO2Me) (PMe3)
2

Ti Me2 (5  C5 H 5 ) 2  Ti (  1-O2 SMe)2 (  5-C5H5)2


2SO 2

 78º C
(iii) Although NC, CO are isoelectronic but its insertion is not extensively
studied :
R
C
Ti R (OEt2) (  5-C5H5)2 + Ph – N  C  (  5-C5H5)2 Cu
N
Ph

(R = Me, Ph, O-C6H4, Me)

44
1.4 Organo Copper in Organic Synthesis

Until 1970's organomagnesium, organolithium, and to a lesser extent,


organocadmium derivatives were the main organometallic systems employed in
organic synthesis. The field of organocopper chemistry has grown
drammatically during the past two decades. In fact, these reagents have become
so important that modern textbooks on introductory organic chemistry expose
students to organocopper chemistry.
The reagent adds selectively at the   carbon of an ,  - unsaturated
carbonyl system, and also has a unique ability to effect replacement of most
types of halogen atoms by methyl groups. Lithium dimethylcuprate reacts with
allylic acetates by an SN2 mechanism. It has been found to react with epoxides
to give open ring alkylated alcohols. It also adds to acetylene esters. In addition,
there are examples of similar reactions involving branched alkyl, phynyl and
vinyl copper reagents. Several specific examples are mentioned below; the
chemical reactivity displayed by the cuprate reagents is due to a powerful
nucleophilicity toward carbon, along with a strong preference for reaction at
alkene or halide site compared to carbonyl groups.
The most important organocopper reagent is lithium dimethyl cuprate,
which is prepared by the action of methyl lithium with cuprous iodide :
4 LiCH3 + Cu2I2  2 Li (Cu (CH3)2] + 2 Li I
This reagent has many characteristics, e.g.
(i) Strong nucleophilicity towards carbon atom and very high affinity
towards alkene and halide positions, as compared to carbonyl group
results in many new reactions,
(ii) Inertness towards groups like cyano or ester present in acid chloride
molecule give special products,

45
(iii) In, ,  - unsaturated carbonyl systems, it selectively attaches with  -
Carbon atom,
(iv) It has special ability to replace various types of halogen atoms by methyl
group,
(v) It reacts with allytic acetate by SN-1 reaction.
(vi) Reacts with epoxides to form open ring alkylated alcohols, and
(vii) It adds to acetylene-esters
The specific reactions of LiCu Me2 with reference to organic synthesis,
are :
1. Halogen Substitution
(i) trans PhCH = CH Br + Li Cu me2  trans PhCH = CH Me
(ii) C6H5I + Li Cu me2  C6 H5 Me
(iii) C5H11 Br + Li [Cu But2]  But (CH2)4 CH3

2. Conjugated Additions
O O
(i) Me CH = CH C Me + Li Cu Me2  Me2 CH CH2 C Me

46
3. Alkylation of Allyl Acetate
Me2 C – CH CH CH2 But + Li Cu Me2  ButCH = CH CH2 But

OOCMe

4. Alkylation of Epoxides
OH

(i) CH3CH2 + Li Cu Me2  CH3 CH2 CH CH2 CH3


Me

(ii) Me CO2 Et + Li Cu Me2  MeCH CH COO Et

OH
5. Formation Ketone from Acid- Chloride
O O
(i) N  C(CH2)10 C Cl + Li Cu Me2  N  C(CH2)10 C Me
(ii) But C Cl + Li Cu Pr42  But C prt

47
Check Your Progress – 2
Notes : (1) Write your answers in the space given below.
(2) Compare your answers with those given at the end of this
unit.
(a) (i) The unstability of transition metal hydrocarbyls is due to
................................ of the metal atom.
(ii) On the basis of ......................................... of the metal atom,
the nature of metal hydrocarbyl varies from ..........................
to ...................................
(iii) Abscence of ......................... or/and presence of .....................
atom increases the stability of metal hydrocarbyls.
(iv) The hydrocarbyl formed in the lower oxidation state of the
metal have very high tendency ................................................
(b) (i) Metal hydrocarbyls decompose by three processes
(x) -------------------------------------------------------------------------
(y) -------------------------------------------------------------------------
(z) -------------------------------------------------------------------------
(ii) During   elimination, alkyl compound decomposes with
transfer of ........................ ion, along with elimination of an
..........................; while   decomposition, due to ..................
mechanism, proceeds with ............................... mechanism in
which the intermediate product is ...........................................
(iii) The example of   elimination is (Equation only)
.............................................................................................
(c) The synthetic applications of organocopper are due its following
characteristics :
(i) Strong ..................and very high .......... positions, as
compared to carbonyl group.
48

.............................................................................................
(ii) ................................ towards groups like ............................ or
................................ present in acid – chlorides.
(iii) In ,  unsaturated systems it selectively attaches .................
(iv) Reaction with allylic acetate is ............................................
(v) Reacts with epoxides to form .............................................
.............................................................................................

1.5 LET US SUM UP

After going through this unit you would have achieved the objectives
stated earlier in this unit. Let us recall what we have discussed so far :
 Organometallic compounds are organic compounds of metals. In these
compounds metal – carbon bond is present. Because organic compounds
are hydro carbons or their derivatives, hence in organo-metallic
compounds, generally those compounds are included in which one or
more hydrocarbon radicals are directly linked with metal atom.
 Compounds of metals with alkyl radicals are called metal alkyls, while
those with aryl radicals are known metal-aryls (i.e. hydrocarbyls).
 Almost all metals of periodic table form hydrocarbyls. For a long time it
was considered that transition metal hydrocarbyls are unstable compared
to their main group analogues. However the unstability is not
thermodynamic but is of kinetic nature.
 Metal alkyl and aryls are named according to IUPAC nomenclature, thus
Zn (C2H5)2 is diethyl Zinc (II), and Me3 Pt Cl is chlorotrimethyl Platinum
(IV).

49
 On the basis of nature, bonding and structure organotransition metal
compounds are classified in to following three groups:
(a) Ionic,
(b)   bonded covalent and
(c)   bonded covalent Compounds

 Ionic organometallics are given by strongly positive s-block metals. In


these compounds, hydrocarbon radical is present in the form of carbo
anion.
   bonded covalent organometallic compounds are generally formed by
metals having 18 electrons or nearly 18 electron- sub shell of d block
metal of group 11 and 12, and p-block metals of groups 13 to 16. while
  bonded organometallics of transition metals with incomplete d-
orbitals are generally unstable.
   bonded covalent organometallics are given by transition metals with
unsaturated sub-shells with hydrocarbon radicals.
 On the basis of types of ligands present these alkyls or aryls are classified
as homoleptic or heteroleptic metal hydrocarbyls.
 Homoleptic MRn, have all the organic groups on the metal atom are
same e.g. TiMe4, V Ph6 etc.
 Heteroleptic, MR n-x [LX], are those metal hydrocarbyls in which the
groups attached to the central metal atom are more than one type e.g. Ti
Me4-x [LX]; Zr M(O Ph) 4-n etc.
 For making synthesis of transition metal alkyls and aryls possible by
stabilizing them, the following measures are taken :
1. Use of alkyl (or aryl) radicals with no  hydrogen,

50
2. Use of radicals like t butyl or isopropyl having crowded  -
hydrogen atoms,
3. In place of  - carbon, use of radicals with Si, Ge and Sn atoms,
and
4. Use of stabilizing agents.
 For preparation of hydrocarbyls of transition metals of different groups of
periodic table, the following methods are generally used: (1) Halide
exchange, (2) Ylide synthesis (3) Transmetallation, (4) Insertion of metal
hydride alkene, (5) Action of anionic metal complexes with organic
halides, and (6) Elimination reactions.
 Alkyl and aryl radicals resemble with hydrogen and halogens in the
presence of unpaired electron. Thus they are mono hapto ligands similar
to hydrogen and halogen and combine with metal atom to form metal
alkyl and metal aryls.
 During synthesis of transition metal hydrocarbyls, with the increase in
electroneutrality tendency, increase in M  L , back bonding ( M  L ,  -
bonding) is seen. This stabilises the compound.
 Similarly, coordination-unsaturation in transition metal hydrocarbyls
results in tendency for polymerisation.
 Alkyls (or Aryls) of transition metal, due to coordination- unsaturation,
are kinetically unstable. They decompose using one of the three
pathways:
(i) transfer of substituent from   bonded hydrocarbyl radical to
metal atom,
(ii) Intermolecular elimination, and
(iii) homohytic fission of M-C bond.

51
 In   elimination, one substituent, R, from   bonded alkyl radical is
transfer to metal atom, along with the elimination of a carbene molecule.
This phenomenon is less seen in transition metal alkyls.
 In   elimination, alkyl molecule decomposes with the transfer of
hydride ion along with elimination of an alkene molecule.
 The important reactions of these compounds are classified in to six
groups :
(i) Decomposition of metal-carbon bond :
TiMe4 + 4 Me COOH  Ti (O2 C Me)4 + 4 CH4
ROR

(ii) Elimination of alkene :


Pt Cl (CH2CH3) (PEt3)2  Pt HCl (PEt3)2 + C2H4
(iii) Transfer of hydrocarbyl radical :
[Pd Me2 (bipy)] + 2 C3 H7 I  [Pd(C3 H7)2 (bipy)] + 2 CH3I
(iv) Formation of addition compound :
[MnR2]n + TMEDA  MnR2 [TMEDA]
(v) Rearrangement reaction :
2 Ni (R) (PEt3)2  NiR2 (PEt3)2 + Ni (PEt3)2 + R - R
(vi) Insertion in M-C bond :

CP R Cp R
Zr + CO Zr
CP R Cp C R
O

 The field of organocopper chemistry has grown drammatically during the


past two decades. The most important copperorgano reagent is lithium

52
dimethyl cuprate, which has many important characteristics which prove
it a better synthetic reagent :
(i) In ,  unsaturated carbonyl systems, it selectively attaches with
  carbon atom

(ii) Inertness to wards groups like cyano or ester present in acid


chloride molecule give special products.
(iii) Strong nucleophilicity towards carbon atom and very high affinity
towards alkene and halide positions, as compared to carbonyl
group, results in many new reactions.
(iv) It has special ability to replace various types of halogen atoms by
methyl group.
(v) It reacts with allylic acetate by SN-1 mechanism.

1.6 Check Your Progress : Key

1. (a) (i) alkyl and aryl derivatives


  bonded

Chlorotri methyl Platinum (IV)


(ii) (1) Homoleptic (e.g. TiMe4 and UPh6; G.F. MRn) and
(2) Heteroleptic (eg ZrMen (OPh) 4-n; G.F. MRn-x Lx).
(iii) The number of carbon atoms of organic moiety which are
within the bonding distance of metal.
(b) (i) Highly unstable
Synthesis difficult task
(ii) Difficulty
Kinetic
(iii)   hydrogen elimination

53
(c) (i) MCl4 + 4 LiMe  MMe4 + 4 LiCl
(ii) 2 TiCl4 + ZnMe2  2TiCl3Me + ZnCl2
(iii) ZrCl4 + n Me3P = CH2  Zr Cl4 (CH2 PMe3)n
2. (a) (i) Coordinate unsaturation
(ii) Electronegativity
Purely ionic to purely covalent
(iii) Hydrogen
F, Cl or O
(iv) Polymerisation.
(b) (i) (x) Transfer of substituent from   bonded hydrocarbyl
radical to metal atom (y) Intermolecular reductive
ilimination (z) Homolytic fission of M-C bond..
(ii) Hydride (H-) ion
Alkene molecule
Homolytic fission
free radical mechanism
four centred.
(iii) Pt Cl (CH2CH3) (PEt3)2  Pt HCl (PEt3)2 + C2H4
(c) (i) Strong nucleophilicity
alkene and halide
very high affinity
(ii) cyano or ester
nertness
(iii)   Carbon atom

(iv) SN1 – mechanism


(v) Alkylated alcohols of open ring.

54
UNIT-2 COMPOUNDS OF TRANSITION METAL-CARBON
MULTIPLE BONDS

STRUCTURE

2.1 Introduction

2.2 Objectives

2.3 Carbene Compounds


2.4 Alkylidene Compounds

2.4.1 Synthesis Methods

2.4.2 Bonding and Structure


2.4.3 Reactions

2.4.4 Applications in organic Synthesis

2.5 Alkylidyne Compounds


2.5.1 Synthesis Methods

2.5.2 Bonding and Structure


2.5.3 Reactions

2.5.4 Applications in Organic Synthesis

2.6 Fischer Carbene

2.6.1 Synthesis Methods


2.6.2 Bonding and Structure

2.6.3 Reactions

2.6.4 Applications in Organic Synthesis

2.7 Let us Sum up

2.8 Check your Progress : The Key

55
2.1 INTRODUCTION

It is interesting to note that the first derivative W(CO)5 {C(OMe)Ph}, in


which carbon is bonded to a transition metal by a double bond was made as
early as 1964 by E.O. Fischer and A. Maasbol and this marked the beginning of
the development of the chemistry of compounds containing transition metal-
carbon multiple bonds. Such compounds in which divalent carbon is bound to a
transition metal are known as carbene complexes; likewise compounds in
which a transition metal is attached by triple bonds with monovalent carbon
moiety are termed as carbyne complexes. While the complexes in which
carbon is attached with only metal atoms are called carbido complexes. In most
of the earlier examples of the carbene complexes, the transition metal was in a
low oxidation state and the derivatives incorporating a hetero atom like O, S or
N on the carbene carbon atom e.g., Cr(CO)5 {C(OMe)Me}, W(CO)5
{C(SMe)Me}, Cr(CO)5 {C(NMe2)Me}, etc. were comparatively more stable.

In 1973, a new class of organometallic compounds having metal-carbon


triple bonds, e.g., M(≡ CR) (CO)4X (M=Cr, Mo, W;R = Me, Et, Ph; X = Cl, Br,
I) was discovered by Fischer and coworkers, ten years after the discovery of
carbene complex.

The chemistry of organometallic compounds having multiple metal


carbon bonds has undergone remarkable transformation during the last three
decades, incorporating ingenious experimental procedures and novel
compounds. These complexes are generally of two types: (1) Carbene (or
alkylidene) complexes: compounds, in which a metal is bound to a carbon atom
by a double bond, are known as carbene complexes; and (ii) carbyne (or
alkylidyne) complexes: derivatives having metal-carbon triple bonds are termed

56
as carbyne (or alkylidyne) complexes (the systematic (IUPAC) nomenclature of
these two classes of compounds uses the suffix-ylidene or – ylidyne
respectively.

In this unit we shall study alkylidene, alkylidyne and fischer carbenes. In


the end of the unit we shall also analyse the applications of these compounds in
organic synthesis.

2.2 OBJECTIVES

The main objective of this unit is to study nature and behaviour of


compounds with metal carbon multiple bonds. After going through this unit you
should be able to:

 know what are carbene, carbyne and carbido, complexes.


 analyse methods of synthesis of alkene, alkyne and allyl complexes.
 discuss nature of bonding and structures of these complexes, and
 describe various characteristic reactions of these compounds.

2.2 CARBENE COMPOUNDS

The carbene complexes are subdivided into two categories:

(i) Heterounclear carbene derivatives: These are complexes of the general


type LnM[:C(R')R"] having one or two electronegative heteroatoms
bonded to the carbene carbon, which endows an electrophilic character
on the carbene carbon. These are generally in low oxidation states and
comparatively more stable and continue to be called as Fischer type (after
the discoverer); and

57
(ii) Homonuclear carbene derivatives: These are compounds with the
metals in high oxidation states and further in these, the carbene which is
bound to hydrogen and carbon atoms only is nucleophilic in nature.
Discovered by R.R. Shrock in 1974, these can be more appropriately
termed as alkylidene complexes in view of the homonuclear nature of the
ligands involved. After the discoverer, these are also called Shrock
Carbenes.

1. Fischer Carbene

The first carbene complex was synthesised in 1964 by fischer ad Maasbol


using the following reaction:

W(CO)6 + RLi W(CO)5 (COR)] Li (CO)5W=CR-OMe

Hexa Carbonyl methyl Lithium Carbene Complex

With the use of alkylating agents like R3O+, BF4- or MeOSO2F etc. in
place of diazomethane (CH2N2), now synthesis of these compounds has become
quite easy. By now a large number of compounds have been synthesised. In
these compounds metal is in low oxidation state and on carbene cabon -
accepting auxillary ligand and substituents are linked. In its reactions carbene
carbon behaves as an electrophilie. In these Fischer – carbenes, structure of
carbene carbon may be represented as follows:

58
2. Shrock Carbene

The homonuclear carbenes, with the general formula LnM[=C(R)R'],


where R and R' are alkyl radicals or hydrogen atoms, were discovered by
shrock in 1974. In contrast to fischer carbenes, these are nucleophilic. The first
Sckock carben was synthesised by the following reaction.

H
Ta(CH2CMe3)3 Cl2 + 2LiCH2 CMe3 CMe4 + (Me3C CH2)3 Ta=C
+2 LiCl
CMe3

Shrock carbenes are given by earlier metals in transition series in their


higher oxidation states. The carbene carbon, in these compounds, is linked with
non  - accepting auxillary ligands and non  - donating substituents. The two
orbitals on carbene carbon have un-paired eletrons, which overlap with two
orbitals of the metal atom:

While, the electrophilic property of Fischer – carbene may be represented


by following reaction,

59
The nucleophilic property of Shrock carbene may be represented by:

(5-C5H5)2 MeTa = CH2 + AlMe3 (5-C5H5)2 MeTa = CH2AlMe3

In a number of reactions these carbene behave as witting reagents.


During synthesis of oleffins Shrock carbenes are important intermediate
products. As a matter of fact these two groups of carbenes, differ widely, rather
than show similarities. Only similarity between the two group is the presence of
metal – carbon multiple – bond in both.

Homonuclear carbenes like (CO)5 W (= CPh2) are electrophilic, hence are


included amongst Fischer type carbens.

2.4 ALKYLIDENE COMPOUNDS

Homonuelear Shrock – Carbenes are generally called 'Alkylidene


Compounds'. As has been shown, these compounds are formed by metals
placed towards left side of d-block series. The first alkylidene compound was
synthesised by shrock in 1974. The important methods for their synthesis are as
follows:

2.4.1 Synthesis Methods

(i) Deprotonation where a base is used to remove a hydrogen, e.g.:

(a) Action of TiC5H5 on TaCl2Me3:

TiC H
TaCl Me 55  (C H ) TaMe
5 5 2
2 3 2

 Ph C
3

60

2  (C H ) TaMe 
Ph PcH
3 
(C H ) TaMe (CH )   
5 5 2 2 5 5 2 2
 

(b) Action of NaOMe on [(C5H5)2 TaMe2]+:

[(C5H5)2 TaMe2] NaOMe (C5H5)2 TaMe (CH2)

(ii) An 'actual' α-elimination, i.e. conversion of a metal alkyl to a


metal (hydrido) (alkylidene) complex, e.g.:
Na(Hg)

(a) TaCl4(CH2CMe3) + PMe3 TaHCl2(PMe3)3 (CHCMe3)


Na(Hg)
(b) C5H5TaCl3(CH2CMe3) + PMe3 C5H5TaHCl(PMe3) (CHCMe3)

(iii) Intromolecular loss of alkene from a bis(alkyl) complex, induced by


addition of ligand, e.g:

(a) TaCl3(CH2CMe3) + TlC5H5 C5H5TaCl2(CHCMe3) + Me3CCH3


-CMe3
(b) Ta(CH2CMe3)3 Cl2+2LiCH2CMe3 Ta(CHCMe3) (CH2CMe3)3

2.4.2 Bonding and structure

13
In the C n.m.r. spectroscopy the alkylidene carbon resonance is
invariably found at low field (200-300 ppm downfield of SiMe4). Such a large
chemical shift appears to be characteristic of many types of carbon atoms which
are multiply bonded to some extent extent to a transition metal. Another
distinguishing feature of alkylidene complexes is low 1Jchα coupling constant
values (75-100 Hz) found for example, in neopentylidene and benzylidene
complexes having less than 18 valence electrons (e.g. TaCl(CH2CMe3)
(CHCMe3)(η5-C5Me5) = 14e, IJchα = 76 Hz).

61
Further 'H n.m.r signals for hydrogen atoms(s) attached to alkylidene
carbon fall in the range δ – 2 to 12. (The values are lowest for 18-electron
complexes), while the infrared studies provide another interesting feature; the
C-Hα stretching frequency is surprisingly low (2400-2600 Cm-1) in the electron
deficient (< 18e) complexes. (A low value for Vchα correlates well with a low
value for 'Jchα.) Based on these physicochemical data. The alkylidene complexes
are defined as compounds in which an sp2 dybridized carbon donor atom also
has a vacant p-orbital which which permits a back – bonding interaction with
filled orbitals on the metal. (Fig 2.1.)

Fig. 2.1. Bonding in metal carbene (alkylidenc) complexes.


It may be noted that the true M-C bond order in such complexes would
usually be substantially less than two. Two typical structures of alkylidene
complexes are shown in Fig. 2.2.

Fig. 2.2.

62
2.4.3 Reactions
Alkylidene complexes (M=CRR') are chemically very labile and the
carbon atom bound to the metal exhibits a strong nucleophilic character,
whereas metal centre is electrophilic. The chemical and spectroscopic studies
show that M=C bond, due to low electronegativity of metal atom (placed at left
side in d-block series), is polarised such that the carbon atom attached to metal
develops negative charge. Corresponding molecular orbital explainations show
that pz orbital of CR2 group is of lower energy compared to dx orbital of metal
atom. As a result, π electron density concentrates on carbon atom. Thus, this
shows strong nucleophitic propery, while the metal atom remains electrophilic.

Fig. 2.3.
The reactions of these compounds are divided in to three groups.

(a) Reactions of nucleophilic carbon.

(b) Reaction with unsaturated organic compounds, and

(c) Decomposition reactions.

(a) Reactions of nucleophilic carbon.

(i) The alkylidene complexes (mainly of Nb and Ta) are strongly


nucleophilic, and therefore, exhibit greater tendency towards protonation
reactions, e.g.:

63
low temp.
(Me3CCH2)3 Ta(:CHCMe3)+HCl TaCl(CH2CMe3)4

(iii) With Lewis acids such as Al2Me6 also, these form addition complexes,
e.g.:


Cp 2Ti ( CH 2 ) Me  Me3 SiBr [Cp 2Ti(CH 2 Si Me3 ) Me] Br 

(C5H5)2TaMe(:CH2)+1/2 Al2Me6 Mel TaMe(CH2AlMe3) (C5H5)2

(iii) Interactions with organic halides have been shown to proceed via SN2
mechanism, e.g.:
Mel
TaMe(:CH2)(5-C5H5)2 TalMe((5-C5H4) ((5-C5H5)2

(iv) Addition with phosphine ligands - Unsaturated phosphine ligand


(Nucleophilic) adds to electrophilic metal centre:

TaMe( CH 2 ) (CHCMe3 )  2PMe3  (Me3CCH 2 ) Ta ( CHMe3 ) ( PMe3 ) 2

(iv) Reaction with carbonyl compounds (Result of combined effect of


nucleophilicity of alkylidene carbon and oxygen affinity of metal centre);
eg. reactions of (Me3CCH2) Ta (=CH CMe3) (PMe3)2 :

(i) Reaction with aldehyde

Me3C CH 2 3 Ta CH CMe3   PhCHO  PhCH  CHCMe3  Me3CCH 2 3 TaO

(ii) Reaction with Ketone

Me3C CH 2 3 Ta CH CMe3   Me2 CO  MeC  CHCMe3  Me3CCH 2 3 TaO

64
(iii) Reaction with Ester

Me3C CH 2 3 Ta CH CMe3   Me2CO2 Et  Me3CCH 2 3 TaO  EtO MeC  CHCMe3

(iv) Reaction with CO2 :


Me3C CH 2 3Ta CH CMe3   CO2  Me3CCH  C  CHCMe3  Me3CCH 2 2 Ta ( O)OH

(b) Reaction with Unsaturated Organic Compounds


In view of their proposed role in alkene metathesis reactions the
interactions of unsaturated compounds with alkylidene complexes
assumes special significance:

(c) Decomposition reactions. The alkylidene complexes are more labile even
at room temperature, that they undergo decomposition reactions.

65
2.4.4 Applications in Organic Synthesis
The reactions given in section 2.4.3 indicate clearly that alkylidene
complexes may be utilise in organic synthesis. The most important reactions in
this respect are:

(i) Alkene – exchange and addition reactions of unsaturated organic


compounds, and

(ii) Reactions with different carbonyl compounds


(See, 2.4.3 (b) and 2.4.3 (a) (v) reactions)

CHECK YOU PROGRESS – 1

Note : (1) Write your answers in the space given below.

(2) Compare your answers with those given at the end of this unit.
(a)(i) Compounds with metal-carbon double bond are known as .............
complexes, while those with metal-carbon triple bond are called
............... complexes. IUPAC names of these compounds are .................
and .................. organometallics respectively.

66
(ii) The general formula of fischer carbene is .................... and that of shrock
carbene is .................... where R = R' = ................ .

(b)(i) Alkylidene compounds are formed by metals placed .................... d block


series. First compound was synthesised in ................. by ..............

(ii) Alkylidene compounds readily give protonation reactions, because their


nature is strongly .............. while, their reaction with organic halides is
............... reaction.

2.5 Alkylidyne Compounds

The alkylidyne or carbyne ligand, a monovalent carbon species [:C-R]+,


with two empty p-orbitals is capable of accepting electron density in a
typical -acceptor fashion, from a metal as well as functioning as a -
donor. Since the alkylidyne or carbyne has two empty p-orbitals, two sets
of metal -electrons can be accepted leading to a formal bonding of the
type, [(OC)5 Cr  CR]+.

2.5.1. Synthesis Methods

1. The historical method :


The first carbyne complex was accidentally synthesized (in 1973) when
an attempt to replace methoxy group from a complexed carbene by halide ion
(from boron trihalide) resulted instead into a carbyne complex :
pentane
M{C(OMe)R}(CO)5 + BX3 low temp. MX (CR) (CO)4 + BX2 (OMe)+ CO
(M = Cr, Mo, W; R = Me, Et, Ph; X = CI, Br, I)

The above reaction procedure has been extended by using AI 2C6, GCl3,
or, AI2Br6, or PBr2 PH3 instead of BX3, e.g.,

67
pentane
W{C(OMe)Ph}(CO)5 + Al2Br6 - 300C
WBr(CPh) (CO)4+ CO
+ Al2Br5(OMe)
- 500C
W{C(OLi)Ph}(CO)4 + PBr2Ph3 WBr(CPh) (CO)4+ CO
+ LiBr + P(O)Ph3

2. Fission of M M Bond :
Interactions of compounds of the type (RO)3 WW(OR)3 with
acetylenes, R'CCR', unexpectedly yield carbne complexes via cleavage of
acetylenes :

(RO)3 W W(OR)3 + R'CCR  2(RO)3 W  CR'


(R = CMe3 ; R' = Me, Et, Pr)

3. From precursor of alkylidene :


Another synthetic route of greater utility uses carbene precursors:
H

 5

 C5 H 5 Cl2 Ta  C
 (i) PMe3
Ph (ii ) Ph3 P  CH 2
( 5  C5 H 5 ) ( PMe3 )CITa  CPh

or

4. From Metal Halides :


The interaction of MoCl5 and WCl6 with neopentyllithim (LiCH2CMe3)
yields the dimeric species [M(CH2CMe3)] ( C – CMe3)]2 with bridging
carbyne ligands. The dimer dissociates into monomeric carbyne complexes :

68
5. From Metal Alkoxides :

A higher yield route to W(CCMe3) (CH2CMe3) consists of the reaction


between WCl3(OMe)3 with six equivalents of bis (neopentyl) magnesium :

WCl3 (OMe)3  _ 6Mg (CH 2CMe3 ) 2 ether


 W ( CCMe3 )(CH 2CMe3 )3

6. The reaction of WCl4 with Hg(CH2SiMe3)2 or MgX(CH2SiMe3) yields a


birdged carbne :

2.5.2.: Bonding and structures


The metal-carbon bond in these carbyne complexes, M  CR, could be
expected to significantly short with the bond angle M – C – C equal to  1800.
While the X-ray structural studies have generally confirmed the former,
variation has been found in the observed M – C– C angle in some cases. In
these alkylidynes donor carbon is sp hybridised, the vacant orbitals help in

69
formation of a triple bond with metal. Out of these,  bond is towards the metal
atom, while two π-bonds are metal dπ –ligand pπ-bonds. Structures of a few
typical complexes are illustrated in Fig. 2.4. and 2.5.

Fig. 2.4

Fig.2.5.

2.5.3. Reactions
There are two important reaction of alkylidyne complexes, which are
used in organic synthesis as catalyst :
1. Synthesis of new alkynes (Exchange Reaction) :

W (C CMe3 )(OC Me3 ) 3  RC  CR W ( CR)(O CMe3 ) 3  RC  C CMe3


Excess

CMe
2. Insertion Reaction
W (C CMe3 )(dme) Cl 3  Me C  C Me  Cl 3 W Me

Me

70
2.5.4. Application in Organic Synthesis
The reactions given in section 2.5.3. are important with reference to
application in organic synthesis.
2.6. FISCHER CARBENE

A large number of such Fischer type complexes are now known for a5 
d8 metals (usually in 0 or + 1 formal oxidation states, assuming the carbene to
be a neutral two electron ligand).

These Fischer type complexes are 18 electron species with the metal in
formally 0 or + 1 oxidation state, these are also characterized by having at least
one stabilizing resonance form and in showing reactivety at C-carbene with
necleophiles.

2.6.1. Methods of synthesis :

Transition metal carbene complexes (Fischer Type) have generally been


obtained from three classes of precursors (starting materials) :

1. Compounds with M-C bond.

2. Metal – Carbene Compounds, and

3. Alkenes.

a) Synthesis from metal-carbon compounds : The most useful general


route for the synthesis of carbene complexes from non-carbene
precursors involves the nucleophilic attack on the carbonyl carbon of a
metal carbonyls, thiocarbonyls, isocyanides or disulphides :

71
(i) From coordinated Carbonyls :
OLi
W (CO) 6  LiR  (OC) 5 W  C R

(R = Me, Ph, etc)


[Me3O]+[DF4]
OMe
(OC)5 W = C R

The synthesis has later been extended to a number of other transition


metals (e.g., Cr, Mo, Mn, Fe, Ru and Re).

(ii) From coordinated thiocarbonyls :

(iii) From Coordinated isocyanides :


cis  Cl 2 ( Et 3 P) Pt  CNPh  EtOH  cis  Cl2 ( Et 2 P) Pt  C (OEt ) ( NHPh)

[ Pt (CNMe) 4 ]2  4MeNH 2  [ Pt (: C{NHMe}2 ) 4 ]2

(iv) From coordinated carbon disulphide derivatives :


Os( 2  CS 2 ) (CO) 2 ( PPh3 ) 2  2MeI  OsI2 (CO) 2 ( PPh3 ) 2 {: C (SMe) 2 }

Pt ( 2  CS 2 ) ( PPh3 ) 2  2MeI  PtI ( PPh3 ) 2 {: C (SMe) 2 } I

72
2. From Metal – Carbene Compounds :

(i) Protonation of methyl group of metal-methyl carbene :

(OC) 5 Cr{: C (OMe) R }  HA  (OC) 5 Cr{: C ( A) R}  MeOH

(Where R  Me, or Ph, and HA  NH 3 , NH 2 Me, NHMe2 , HN : CPh2 , R' SH , etc.).

(ii) Transfer of Carbene ligand :


(OC) 5 W {C ( X ) Ph} Au ( H )Cl4 heat

 Cl  Au{: C ( X ) Ph}  WCl2 (CO) 4

( X  OMe, NH 2 , NMe2 )

or Cp( NO) (OC)Me{: C ( R) Ph}  Fe(CO) 5 


hv
Mo(CO) 2 ( NO)CP  (OC) 4 Fe{: C ( R) Ph}

(iii) Displacement of neutral or anionic ligands :


Synthesis of new transition metal carbene complexes can be achieved via
displacement of either neutral or anionic ligands from parent transition metal
carbene derivatives :

Or ( P.Ph3 ) 2 Cl3 Rh{: C( N Me2 ) H }2PEt 3  ( PEt 3 ) 2 Cl3 RH {C( NMe2 ) H } 2PPh3

3. Cleavage of electron – rich alkenes :

This is a remarkable, quite general route to the synthesis of diamino-

73
substituted carbenes, and involves interaction of various metal derivatives with
highly electron rich alkenes such as the bis(imidazolidizidene) mono, bis,
neutral, and cationic carbene derivatives involving a majority of the transition
metals have been prepared by this procedure :

(i) By the action of metal carbonyls :

(ii) Reaction with metal phosphines :

2.3.2 Bonding and structure


In these carbons the M-CRR' grouping is always planar, and the M-C
distances indicate considerable shortening in length which is in conformity with
their multiple bond character. The CO and CN bond distances are also

74
shortened in view of the -bonding involved.
The carbene group : C(OMe)Ph is a monohapto ligand which provides an
electron pair to the metal tungsten for a -bond formation. The alkylidene
ligand may have (Fig.2.6.) either of the conformations singlet (a) or triplet (b).
The vacant px and py orbitals in the two conformations respectively could be
expected to form -bonds with px and dxz orbitals of the metal (W) in the latter
case. Actually the dxz and dyz orbitals in the complex are of similar energy and
comprise a composite orbital of cylindrical symmetry, making it possible for
the -interaction between the alkylidene and the metal to occur in all planes
intermediate between the dxz and dyz planes. The conformation adopted by the
complex would therefore not depend on maximizing the -bonding, but would
be controlled by the non-bonding interations between the alkylidene ligand and
the nearby carbonyl groups; the conformation would consequently be staggered
to minimize there latter interactions.
Thus, above bonding description reveals that the singlet carbene which
has a filled orbital of -pseudosymmetry and an empty p-obital of -pseudo-
symmentry enter into synergic bonding interactions with transition metals
forming LM -bond and ML -bond, similar to that in case of alkene. (Fig.
2.7.).

(a) singlet state, sp2 (b) triplet state sp


hybridization hybridization
Fig. 2.6. Molecular orbital (MO) diagrams for carbenes.

75
Structures of some carbene complexes are given in Fig. 2.8., a perusal of
which indicates Cr-C distance  2.0A0 and CC distance  1.5 A0, while CO
and CN distances (1.3A0 and  1.8A0 respectively) are also smaller, similar
to MC bond distance. These confirm metal-carbon multiple bond.

Fig. 2.7.

2.6.3. Reactions

As we know in carbene complexes, whre metal ion is nucleophilic,


carbene carbon is electrophilic. These complexes give various types of
reactions:

76
1. Displacement of ligands coordinated with metal :

OMe
(i) (CO) 5 Cr  C (OMe) R  PR3  (CO) 4 ( PR3 )Cr  C
R

Substituti on
(ii) (CO) 5 Cr  C (OMe) R  Py     (CO) 5 Cr Py  CH 2  CH (OMe)
and fission

2. Displacement on Carbene Carbon:


NR'R"
(i) (CO)5 Cr  C (OMe) R  HNR' R"  (CO)5 Cr  C
R

N = CPh2
(ii) (CO)5 Cr = C (OMe)R + HN = CPh2  (CO)5 Cr = C R

Nucleophilic Ph
(iii) (CO) 5 Cr  C (OMe)Ph  Li Ph (CO) 5 Cr  C
Addition Ph

3. Reaction on side chain of carbene:


OMe
(CO)5 Cr = C (OMe)R + HC  CPh (CO)5 Cr = C CH=C(Ph)R

4. Oxidation and Reduction of metal :

77
5. Insertion on double bond

(i)

OMe OMe
(ii) (CO) 5 Cr  C  Ca(CN )  (CO) 5 Cr  N  C  CH
Ph Ph

2.6.4 Applications in Oraganic Synthesis


Carbene complexes are used for synthesis of various organic compounds
by decomfolexation. e.g.

1. Alkene by dimerisation of carbene ligand:

i.

1300
ii. Heat

2. New alkene from decomplexed carbene :

CH2=CHOR
i.
500C

78
ii.

3. Cyclopropene and vinyl ether by the reaction of electro deficient alkene


or diazomethane:

(i)

(ii)

4. Ester from decomplexed carbene by reduction:

79
(iv) Synthesis of special compound containing alkyle, carbene and
carbyne ligands (Churchill and Youngs, 1979):

CARBIDE OR CARBIDO COMPLEXES:


When all the hydrogen atoms from methane are removed one by one
carbon atom is left in the end:

Atomic carbon when combines with metal atoms only behaving as a


ligand, we get carbido complexes (Fig. 2.9)

First carbido complex was synthesised in 1962, but their extensive


synthesis could only be possible after 1983, when carbon atom is surrounded by
metal atoms it is inert but when it exposed after removing one or more metal
atoms, it becomes active. e.g. (Fe6C(CO)16)2 on oxidation, unshares two iron
atoms (as Fe++) leaving carbon exposed; which reacts with nucleophilic

80
reagents like CO and MeOH:

In reaction (I), the carbide formed from hexa coordinated carbide has
butterfly structure.

The complex formed in reaction (II) on further hydrogenation gives


methyl acetate. The result of this synthesis, gives organic oxygenate analogous
to Fischer – Tropse reaction.

CHECK YOUR PROGRESS-2

Notes: 1. Write your answers in the space given below.

2. Compare your answers with those given at the end of the unit.

(a)(i) In historical method for synthesis of alkylidene complex is :

81
........................................................................................................
(ii) In alkylidyne complexes the two π bonds are from metal
.............................. to ....................... bonds and the bond angle is
approximately .......................

(b)(i) Fischer Carbenes are given by ................ metals in their lower oxidation
states .............. and ..................

(ii) The singlet carbene the σ orbital of pseudo symmetry is ........ and the π
orbital of pseudo symmetry is ............, links with metal atom, analogous
to alkene, forming ..................... and ................. bond.

(C)(i) The important uses of carbenes are in the sythesis of :

(x) .................,

(y) ................. and (z) .................

(ii) An important example of carbido. iron is: .....................

1.7 LET US SUM UP

After going through this unit, you would have achieved the objectives
stated earlier in this unit. Let us recall what we have discussed so far:
 Compounds in which divalent carbon is bound to a transition metal
(with M-C double bond) are known as carbene complexes. Like wise
compounds in which a transition metal is attached by triple bond with
carbon is called carbyne complex. In IUPAC nomenclature carbene
compounds are known as alkylidene compounds, while carbyne
compounds are called alkylidyne compounds.

82
 Carbene compounds are named after the names of their discoverers as
fischer carbenes and shrock carbenes.

 Fischer carbenes are generally heteronuclear carbene derivatives, with


a general formula LnM [=C(R')R"] In these compounds, one or two
electronegative hetero atoms are attached with carbene-carbon. These
carbenes are electrophilic.

 Shrock Carbenes are generally homounclear carbene derivatives with


a general formula LnM [=C(R)R']. Where R and R' may be both alkyl
or hydrogen atoms. These are nucleophilic compounds.

 Homonuclear Shrock Carbenes are called alkylidene compounds.


These componds are synthesised by deprotonation, α elemination and
intra-molecular loss of alkene from a bis (alkyl) complex – reactions.

 In IR spectrum of alkylidene complexes CH bond is shown at lower


frequencies, 2400-2600 Cm-1, indicating metal– carbon multiple
bond.

 In these complexes sp2-hybridised carbon is a donor–atom.

 Due to nucleophilic nature, alkylidene complexes give three types of


reactions:

(a) Reactions of nucleophlic carbon,

(b) Reactions with unsaturated organic compounds and

(c) Decomposition reactions.

83
These reactions are used in organic synthesis.
 Alkylldyne ligands, CH or CR, are monohapto three electron ligands,
which combine with a metal atom forming a triple bond.

 These compounds are synthesised by the historical method,


substitution of methoxy group of carbene complex by halide or by
fission of MM bond, or from precursor of alkylidene, metal halide,
or metal alkoxide etc reactions.

 In alkylidyne compounds there are one σ and two π – bonds between


metal and ligand. σ bond is from ligand to metal, while π bonds are
metal dx – ligand p π bonds.

 The important reactions of these compounds are, synthesis of new


alkyenes and insertion reactions and these are used for organic
synthesis.

 Fischer carbenes are formed generally by d5-d8 metals in their lower


oxidation states, 0 or +1.

 Free carbene is found in both signlet and triplet states. In signlet state
sp2 hybridisation is used. Electron pair is present in a sp2- hybrid
orbital while in triplet state, sp-hybridisation is utilised. One electron
each is present in the two unhybridised p-orbitals.

 The important reactions of these compounds are:

(i) Substitution of ligand coordinated with metal.

(ii) Substitution of carbene carbon.

(iii) Action of side chain of carbene.

84
(iv) Insertion on the double bond.

(v) Oxidation or reduction of metal etc.

 These compounds are used in the synthesis of alkene, ether and esters.

 In carbido complex four metal atoms are linked with carbon atom. An
important carbido complex is carbido-iron, C(Fe)4 which has a
butterfly structure.

1.8 CHECK YOUR PROGRESS: THE KEY

1.(a) (i) Carbene Complex


Carbyne Complex
Alkylidene
Alkylidyne

(ii) LnM[=C (R')R"]


LnM[=C (R)R'] (R=R'=alkyl radical or Hydrogen)

(b) (i) Placed towards left in


1974
shrock

(ii) Nucleophilic
SN-2
2.(a) (i) Substitution of methoxy group from carbene complex by halide
ion.
(ii) d π, orbital
Ligand p π
180o

85
(b) (i) d5 – d8
0
1
(ii) Filled
empty
L→M, σ – bond
M→L, π – bond
(c) (i) (x) Alkene (y) Ether and (z) Ester
(ii) C (Fe)4

86
UNIT-3 TRANSITION METAL -COMPLEXES-I

Structure :

3.1. Introduction

3.2. Objectives

3.3. Alkene Complexes


3.3.1. Methods of preparation
3.3.2. Bonding and structure
3.3.3. Reactions
3.3.4. Catalytic Reactions

3.4. Alkyne Complexes


3.4.1. Methods of Preparation
3.4.2. Bonding and Structure
3.4.3. Reactions

3.5. π3 – Allyl Complexes


3.5.1. Methods of Preparation
3.5.2. Bonding and Structure
3.5.3. Reactions

3.6. Let us Sum up

3.7. Check Your Progress : The Key

87
3.1. INTRODUCTION

Although the formation of potassium ethylenetrichloro-platinate (II),


K[PtCl3(C2H4)], by the action of ethylene on a solution of potassium
chloroplatinate (II) was noted by Zeise as long ago as 1830. The chance
discovery of ferrocene in 1951 may be said to mark the beginning of a period of
intense activity.

-bonded oganometallics of transition metals are much more common


and occur in a variety of fascinating structural patterns. In fact the interactions
of the orbitals of unsaturated hydrocarbons with these metals often bring about
such novel and non-classical types of bounding, which do not have a
counterpart elsewhere in chemistry. In view of the lability of many such
species, they play an important role in the catalytic reactions of alkenes,
alkynes, and their derivatives. Many of these catalytic reactions involves
transition metal-carbon monoxide bonding, the nature of which is in some ways
similar to that in -bonded organometallics ; both of these generally follow the
Sidgwick effective atomic number (EAN) or18-electron rule.

In classifying further hydrocarbon complexes it is generally convenient


to consider the number of electrons formally available (without reference to
whether they are involved or not, which can only be inferred from the structure
of the complex) from the neutral hydrocarbon or hydrocarbon radical. Thus we
have, with increasing numbers of formally available electrons, the following :

(i) Alkene and Alkynes organometallic; two electron donors,

e.g., Pt Cl 3 ( 2  C2 H 4 ); Pt ( PPh3 ) 2 ( 2  C 2 Ph2 ) .

88
(ii) Allylic organometallics ; three electron donors, e.g., Ni ( 3  C3 H 5 ) 2

(iii) Diene organometallics; four electron donors,e.g., Fe (CO) 3 ( 4  C 4 H 4 )

(iv) Cyclopentadienyl organometallics; five electron donors,


e.g., Fe 5  C5 H 5 2

(v) Arene Organometallics; six electron donors,


e.g. V  6  C6 H 6 2 ; Cr  6  C6 H 6 2

In this unit we shall discuss 2 – hapto and n3-hapto complexes. At the


end of the unit we shall describe applications of these complexes in organic
synthesis, in the light of their chemical reactions.

3.2. OBJECTIVES

The main aim of this unit is to discuss nature of 2 and 3 - -bonded


organometallics. After going through this unit you should be able to :

 understand how these organometallics are classified on the basis of


number of electrons used in bonding.

 describe method of preparation of these 2 – (Alkene and alkyne) and 3


– hapto (allyl) roganometallic compounds.

 explain their structures on the basis of bonding in these complexes, and

 discuss their applications in organic synthesis in the light of their


characteristic reactions.

89
3.3. ALKENE COMPLEXES

The complexation of alkenes with transition metals (in which C = C


double bond contributes two electrons) has aroused considerable interest
(theoretically and practically) since early fifties. The alkene-metal bond involve
both -donor and -acceptor linkages of these ligands, which appear to play a
synergetic role on the strength of these bonds. The bonding of alkenes to metals
has been shown to be similar to that in metal carbonyls ; both the ligands are
two electron donors and in fact, the replacement of carbon monoxide in metal
carbonyls by olefins provides a versatile route for the synthesis of the latter type
of compounds. Again, derivatives of the alkenes are also generally more stable
with the metal in low oxidation state and are governed by the simple E.A.N.
rule of Sidgwick.

Only the latter transition metals (especially in their lower oxdation states)
are known to form to form complexes with monoalkenes. Alkene complexes of
transition metals are generally heteroleptic in nature, e.g., Re(CO) 4 (alkene)+,
MoX(CO)2(alkene)3, and Fe(CO)2 (alkene) (5C5H5), although a few
homoleptic derivatives also are known, e.g., Co(2C2H4)n (where n = 1 or 2);
Ni(2C2H4)n, Ni(2C2H4)n and Pd(2C2H4)4 (where n = 1 or 3) have been
isolated in a low-temperature matrix using metal-vapour synthetic procedures.

3.3.1. Methods of Preparations.

(a) Reaction of metal chloride or carbonyl with alkene.

This is a simplest method for synthesis of alkene complexes. Zeise- salt


was prepared by passing ethylene into an aqueous solution of tetra
chloroplatinate :

90
 
K 2 Pt Cl4  CH 2  CH 2  K Pt Cl3  2  C2 H 4  KCl 


M CO6  NC 2 C  C CN 2  M (CO) 5  2  C2 (CN ) 4  CO 
M  Cr , Mo or W

Temp.
MX (CO) 3 (  C5 H 5 )  H 2 C  CH 2 
5

 M (CO) 3 ( 2  C 2 H 4 ) ( 5  C5 H 5 )


Pr es
M=Mo or W

Mn (CO) 3 X  H 2 C  CH 2 140 
 Mn(CO) 3 ( 2  C2 H 4 ) X 
Atoms
 

Mn (CO) 3 ( 5  C5 H 5 )  H 2 C  CH 2 
UV
Mn(CO) 2 ( 2  C2 H 4 ) ( 5  C5 H 5 )  CO

(b) Displacement of hydride ion from coordinated (-bonded) alkyl


ligand (-hydrogen elimination) :

H  CH 3 
   
||
5
 C5 H 5 CO  Fe.CH 2 C CH 3  5  C5 H 5 CO 2 Fe  CH 2  C 
Base (Pr otonation )  OH 

H  CH 
 5

 C5 H 5 CO 3 Mo  CH 2  CH  CH 2  5

 C5 H 5 CO 3 Mo  CH 2  C 
 OH 3

In these reactions organic cations, Ph3C+, R3O etc, have been found quite
useful.

91
(c) Reductive Alkenation

In these reaction addition of alkene also involves reduction of


transition metal to lower oxidation state:

EtOH
RhCl3+C2H4 [{Rh Cl( 2-C2H4)}2]

Ni (acac)2+Al Me3+P(C6H11)3+RCH = CH2 [{Ni ( 2-CH2=CHR)P(C6H11)3}2]

3.3.2 Bonding and structure


Alkenes resemble carbon monoxide in their ability to complexes with
transition metal ions (particularly those with d 8-d10 configurations)
affording a variety of interesting compounds. The nature of bonding in
such complexes has aroused considerable interest.

A more elegant description of bonding in terms of a ,  scheme was


suggested by Dewar (in 1951) for silver (I) olefin complexes and used by
Chatt and Duncanson (in 19563) for platinum (II) complexes. The
molecular orbital approach as developed by Dewar, Chatt and Duncanson
incorporates the ideas; (i) a vacant 5d-orbital of the silver or a vacant
5d6p2 orbital of the platium atom is overlapped by the (bonding)
molecular orbital of ethene to give -type bond (Fig. 3.1(a) and (ii) a -
type bond (Fig. 3.1 b) is formed by overlapping a filled 4d-orbital of
silver atom or a 5d6p-hybrid, orbital of the platinum atom with
antibonding 2'2p molecular orbital of the alkene. In Fig. 3.1 (c), an
attempt has been made to depict the synergic strengthening of the metal-
alkene bonds in such complexes.

92
(a) -Bonding

(b) -Bonding

(c)  and  bonding


Fig. 3.1 CH2 = CH2 Bonding with Pt.

In the bonding scheme described in Fig. 3.1 both donation of -electron


density from the alkene to metal and accumulation of electronic charge in
the olefin antibonding 2*2p orbital would be expected to lower the -
bond order of the coordinated alkene; this has been supported by
bathochromic shifts in the i.r. spectra of alkene complexes as well as by
X-ray.

The influence of coordination (both -and -back donation) processes

93
involved in the formation of metal-olefin complexes results in weakening
of the olefin double bond, which is demonstrated in a lowering in the
v(C=C) stretching by 50-160 Cm-1, For example, the v(C=C) stretching
frequency, observed for free propene at 1652 Cm-1 is lowered by 148 Cm-
1
on complex formation (e.g. in K[PtCl3(2- C3H6)]) to 1504 Cm-1.

The strength of -back bonding of the metal with the alkene depends on
the nature of the other ligands bonded to the metal. The observation that
in complexes of the type, RhL(C2H4)(C2F4) (where L= acac or C5H5), Rh-
C(C2F4) bond distances (2.01-2.02A) are shorter than the analogous Rh-
C(C2H4) bond distances (2.17-2.19A), substantiates the expectation that
the electron withdrawing substituents would enhance the -acceptor
ability (C2F4>C2H4) of a particular alkene.

In general the application of LCAO-MO method to complexes of


transition metals with unsaturated molecules follows the following three
steps, as in the case of complexes of simpler molecules.

Firstly, one has to pick out the valency atomic orbitals of the atoms in the
molecule under consideration. For example, in a transition metal alkene
complex such as Zeise's salt. [PtCl3(H2C-CH2)], the metal valence atomic
orbitals are 5d, 6s and 5p. The ligands may have  and  valence orbitals;
for example, in an alkene the valence orbitals are composed of sp2 hybrid
orbitals and the -valence orbitals are 3pz. These two pz orbitals (one on
each carbon atom), in ethene, on in-phase linear combination, give a
molecular orbital that covers the entire molecule. In the first
approximation the energy or electrons in this -orbital has a value
considerably lower than that of any of the other -electrons. The next

94
higher energy molecular orbital is formed by substraction (i.e. out-of-
phase linear combination) of the two pz atomic orbitals.

The second step involves the process of constructing suitable linear


combinations of valence atomic orbitals for the molecule. For this, a
knowledge of the molecular symmetry is required.

Finally, the molecular oribitals are placed in order of increasing energy.


The advantage of the molecular orbital approach to metal-ligand bonding
is that we can picture the filling of molecular orbitals with electrons in
the order of their energy, irrespective of the origin of the electrons.

Nuclear magnetic resonance studies indicate alkenes are in general non


rigidly bonded to the transition metals and these complexes are,
therefore, often fluxional in nature. Nonrigid attachment of alkenes to
transition metals generally permits rotation either of a barrel-type (i.e. the
rotation of metal-alkene axis as shown in B of Figure 3.2).

The above phenomenon of the non-rigid attachment of alkenes to


transition metals has been investigated for the complex, (5-
C5H5)Rh(C2H4)2 (Fig. 3.2.) by the application of 'H n.m.r. spectroscopy.
the spectrum of the complex was found to vary with temperature (Fig.
3.3). The spectrum recorded at – 19ºC depicts two distinct tyes of
environments about the protons. The protons labelled as Ho (outer)
appear to give the downfield multiplets (d) and the upfield multiplets (u)
could be ascribed to the inner protons, Hi. These discrete signals were
explained on the basis that at the low temperature, the rotation of the
olefin becomes so slow that it does not affect the observation in the n.m.r.
spectrum of the two distinct environments for the rotons in the molecule.

95
However, as the temperature is raised, the rotation of ethene molecule
about the metal-alkene bond tends to make all the ethene protons
magnetically equivalent and the sparate lines collapse into a broad signal.

The predictions from the above theoretical considerations have received


ample support by the actual structures of metal-alkene complexes. For
example, the crystal structures of K[PtCl3(C2H4)] (Zeise's salt) and Pt
[NC)2C=C(CN)2} (PPh3)2 are depicted in Figs. 3.1 and 3.4 respectively.

The C-C bond distance (1.37A) in the complex (Fig. 3.1) is slightly
longer than in the free ethene (1.34A) which can be explained to arise
from the population of electrons in the  orbital of ethene, which brings
about a change in the nature of the hybrid orbitals at carbon atoms. For
example, a perusal of Fig. 3.4 shows that the C-C bond length and (NC)
C (CN) angle in coordinated tetracyanoethylene are increased
considerably with a concomitant change in the sp2 hybridization in the
parent alkene to sp3 type in the complex.

96
Fig. 3.4

Hence these complexes are generally represented as in Fig. 3.5 (a) and
(b) or the resonance hybrid of the two structures.

Fig. 3.5
A considerable amount of X-ray structural data, which has become
available in more recent years, supports the following general conclusions:

a) the C-C bond length in the alkene is increased on complexation.

b) the planar alkene molecule becomes non-planar on complexation with the


substituents bonding away from the metal as well as other ligands,

c) the C-C bond is perpendicular to the molecular plane in 16 electron


molecules of the type ML3 (alkene), e.g., [PtCl3(C2H4)], and.

d) the carbon atoms of the ligated alkene molecules are symmetrically


situated (i.e. equidistant) with respect to the central metal atom.

97
The structures of these complexes are analogous to distorted square,
which generally polymeries e.g. the bis-ethylene complex of rhodium chloride
is a dimer:

After linking with metal, the chemistry of the ligand changes to a great
extent. Free alkene is fond of electrophilic reaction, rather than a nucleophilic
reaction. But after coordinated with metal, ethylene becomes nucleophilic,
perhaps the carbons become more positive.

3.3.3 Reactions
Chemical properties of alkene complexes depend on the following facts:
(a) For metal atoms alkenes are weak ligands hence can be replaced
by strong ligands like cyanide, t-phosphine etc.
(b) After coordination with metal, electron-density in -bonding
orbital decreases, but increases in antibonding * orbital, As a
result alkene molecule is activated and takes part in different types
of reaction. These reactions are important for industries.
(c) 2- alkene complexes give many products using nucleophilic
reactions.

Stoichiometric reactions of transition metal alkene complexes: (i)


Nuclecophilic attack on 2-alkene complexes. The nucleophilic attack can occur
in three different ways: (a) the nucleophile displaces the alkene, (b) the
nucleophile attacks the metal but displaces ligands other than the alkene, and (c)

98
the nucleophile attacks at an alkenic carbon of the alkene. These general types
of reactions are summarized in schemes I to V:

99
Scheme-V

Reactions lnvolving Metal – Alkene Intermediates in Homogeneous


Catalyzed Reactions. The consequence of alkene – metal interaction include a
lowering of the electron density of the  bonding orbital and an increase in the
electron density of the  orbital. The overall effect of alkene coordination a
metal centre brings about excitation of alkene -bonding electrons to the  level
resulting in activation of the alkene molecule, which tends to undergo a wide
variety of reactions, many of which are of great industrial importance. Some

100
typical examples involving metal – alkene intermediates in the homogeneous
catalyzed organic synthesis are illustrated as follows:
(a) Hytdrogenation:

(b) Hydrosilylation:

(c) Carboxylation:

(d) Hydroformylation:

(e) Oligomerisation:

101
(f) Isomerisation:

(g) Dismutation:

3.4 ALKYNE

Although alkyne complexes have been studied less extensively, yet their
chemistry reflects some rather fascinating features. For example, in alkynes the
presence of two -bonds at right angles to each other provides greater
possibility for bonding of alkynes with metals. Of the two -bonds available in
alkynes, either only one or both may be donated to a metal.

The reactions of alkynes with different transition metal species can occur
in different ways. In the simplest cases, alkynes replace only one two – electron
donor ligand from the original complex. In these, only one of the two -electron
pairs of alkynes takes part in the reaction.

Simple alkynes complexes are similar to their alkene analogues. For


example, similar to zeise salt is acetylene complex, in which acetylene molecule

102
is linked in place of ethylene molecule, e.g. L2Pt (RCCR) or (Pt(RCCR)X3)-.
The structure of these complexes are analogous to that of alkene complexes. In
these complexes one of the dsp2 hybrid – orbitals of the metal links with a pair
of electrons from  bond of RCCR. Alkynes are more electronegative
compare to alkenes, hence they are comparatively stronger -acceptor.

Alkynes have two  bonding and two * antibonding orbitals, which are
quite capable of interacting metal orbitals. Out of these one or two electron
pairs may be donated to metal atom. It is assumed that these are utilized in a
mononuclear complex eg. in Mo (Meso. tetra-p-tollyl porphyrin) (HCCH).

The two -bonds in acctylenes are placed perpendicular to each other,


hence these can not function as a bidentate ligand easily. Only in binuclear
complexes these can be utilized for linking two metal atoms, e.g. dicobalt octa
carbonyl when reacts with acetylene, it links as a bidentate ligand replacing two
molecules:

Co2 (CO)8 + HCCH  Co2(CO)6 (C2H2) + 2CO

In this complex two  electron pairs are donated to cobalt atom and
HCCH molecule forms a bridge between two cobalt atoms.

Similar to carbonyl complexes, these complexes also follow EAN – rule.

3.4.1 Methods of Preparation


(i) Simple method of their preparation involve replacement of carbonyl etc.
from metal complexes by alkyne:

(a) M (CO) 6  RC  C R' 


UV
M (CO) 5 ( RC  CR' )  CO
(M  Mo, W )

103
(b) Mn (CO) 3 ( 5  C5 H 5 )  RC  CR  Mo ( RC  CR) ( 5  C5 H 5 ) 2  CO
(c) MC (CO3 ) ( 5  C5 H5 )2  Ph C  C Ph UV


Mn (CO) 2 ( 2 PhC  CPh) ( 5  C5 H 5 )  CO

(d) Fe (CO)5  RC  C R  Fe(CO)4 ( 2  RC  CR)  CO


(e) MH 3 ( 5  C5 H 5 ) 2  RC  CR  MH ( 5  RC  CR) ( 5  C5 H 5 )  H 2
(M  Nb, Ta)

(f) K 2 Pt Cl 4  Bu ' C  C Bu '  [ Pt Cl (M  Cl ) ( 2  Bu 1C  C Bu 1 ) 2 ]  2 KCl


(ii) Reactions in which ethyne molecule replaces two monodeutate
ligands:
V (CO) 4 ( 5  C5 H 5 ) 2  RC  CR V (CO) 2 ( 2  RC  CR) ( 5  C5 H 5 ) 2  2CO

(iii) The two pairs of -Electrons Donated in two Metal Atoms with the
Alkyne Functioning as a Bridging Ligand:

In these reactions generally polynuclear complexes are formed:

The reaction of iron carbonyl with acetylene, RCCR often give special

104
products (Fig.3.6.)

Fig. 3.6
3.4.2 Bonding and structure

Alkynes with two -bonds may bind metals utilizing one or both sets of
-electron pairs, thus providing greater possibilities for bonding by alkynes.

Algthough the boding in alkyne complexes could be easily interpreted in


terms of Dewar – Chatt – Duncanson model, there is structural evidence that
rehybridization occurs to form relatively strong -bonds. As the alkynylide
RCC- is isoelectronic with NC and CO ligands, ' – alkynyl transition metal
complexes containing M-CCR groups, may also be expected to have both -
donor and -acceptor character. (Fig. 3.7 (a))

105
In the formation of a -bond of the above type, the CC bond should be
expected to become weaker; this is reflected in the lowering of the vCC
absorption by about 150 Cm-1 in the metal acetylide compared to that in the free
acetylenes.

Regarding the nature of bonding of ' – alkyne complexes, the Dewar-


Chatt-Duncanson bonding model (Fig. 3.7(b)) appears to be applicable in these
also as in  and * orbitals of which one lies in the MCC plane (" and *
similar to that in alkene analogues) and the other is perpendicular to the MCC
plane ( and *). This latter pair has also symmetry characteristics appropriate
for bond formation with transition metal d orbitals.

Evidence for a tendency toward a C=C double bond in 2 – alkyne


13
transition metal complexes may be obtained from i.r. as well as 'H and C
n.m.r. spectral data in addition to the information received from X-ray
diffraction studies. Some characteristic structure of some complexes are given
in Fig. 3.8.

106
Fig. 3.8 Structure of (a) Pt(PPh3)2(2-PhCCPh).

(b) (5-C5H5)Ni(-PhCCPh)Ni(5-C5H5)

(c) (OC)3Co (-2-PhC  CPh)Co (CO)3

(d) Fe3(CO)9 (2-PhC = CPh)2 and

(e) (5 – C5H5) (OC)Rh(-1CF3CCCF3)Rh(CO)( 5-C5H5)

3.4.3 Reactions
As expected, the reactivity of coordinated alkynes would be to some
extent influenced by the nature of the metal involved. Thus alkyne complexes
of transition metals in low oxidation states generally undergo reactions with
electrophiles, while complexes of transition metals in higher oxidation states as
well as cationic complexes are usually reactive towards nucleophilic moieties.
A few examples of these types of behaviour are illustrated below:

107
(a) Displacement reactions
The displacement of one alkyne by another has been exploited for the
preparation of new alkyne complexes:

Pt ( PR3 ) 2 ( HC  CH )  RC  CH  Pt ( PR3 ) 2 ( RC  CH )  HC  CH

In these reactions the case of alkynes displacement can be represented as:


acetylene < alkylacetylenes < arylacetylenes < nitroacetylenes

The following two reactions represent two types of displacements from


alkyne complexes with reagents other than alkynes:

Pt ( PPh3 ) 2 (CH  CH )  2 PPh3  Pt ( PPh3 ) 4  HC  CH


(excess )

[ PtCl (en)( HC  CH )] Cl 


PtCl 3 ( HC  CH )  en THF

Reaction on double bond of coordinated alkene:

(ii) Alkyne complexes also undergo a number of other interesting reactions,


involving, for example, oligomerization and hydrometallation, e.g.:

CO
RC  CH   [ RC  C  Pd 11] 
Pd ( II )
 RC  CCO2 R
R' OH

Ni (CO) 4
HC  CH  H 2 O      H 2 C  CHCO2 H
150 0 C , 130 atm

PdCl 2 / thiourea
HC  CH  CO  MeOH     MeO2 CCH  CHCO2 Me
O2

108
(b) Reactions with Nucleophiles:

In these reactions the nucleophilic reagent reacts with metal in Cis-form


or with proton of alkyne in trans form:

(c) Reaction with Electrophilies:

HCl
(i) Pt(PPh3)2 (2 Ph C  C Ph)  Pt(PPh3) Cl2 + Ph' CH = CH Ph

109
CHECK YOUR PROGRESS – 1

Notes: (1) Write your answers in the space given below:

(2) Check your answers with those given at the end of the unit.

(a) (i) Alkene and alkynes........................ and ........................................


ligands respectively.

(ii) First 2- dihapto transition metal complex was ............................


salt.

(iii) In Zeise salt  - bonding takes place between ..............................


hybrid orbital of platinum and ................., .................... molecular
orbital of ethylene whereas -bonding takes place due to
overlapping between ................., molecular orbital of ethylene and
..................., orbital of platinum.

(b) (i) The polynuclear complex obtained as a result of reaction between


Fe3(CO)12 and PhCC.Ph is..............................

(ii) In alkyne complexes, bonding is represented according to


.................... method, analogous to ..................... complexes.

(iii) Alkyne molecule behaves as both................ and.......................... .

(iv) During reactions of nucleophiles with alkyne – complexes, the


nuclophile either links with metal atom in............................... or
links with proton of alkyne in ................. .

110
3.5 3- ALLYL COMPLEXES

The preparation of 3 allylic complexes has been one of the exciting


developments in coordination chemistry. The significant feature of the allyl
group, H2C=CH-CH2-, is its dual (mono – as well as tri - hapto) character of
ligaqtion.

A large number of 3–allyl complexes of almost all d' – dx metals in the


three (3d like Ti, Zr, V, Nb, Ta, Cr, Mo, W, Re, Fe, Co, Re, Fe, Co, Rh, Ir, Ni,
Pd and Pt. It is further interesting to note that allylic groups can also act as
bridging ligands.)

Further even when  - allyl group is a part of a larger ligand, it is known


to form 3 – complexes with transition metals. In addition to the 3 bonding
type allylic group can also function as a -ligand or as a , 2 ligand.

In view of the above, one has to be very careful while suggesting the
structures for allylic derivatives. The 18–electron rule is useful in distinguishing
between 3 – and 1-allyl types, but the third type can be identified only by X-
ray structure determination. The , 2 – allyl derivatives are fluxional (cf. unit
8) with the metal changing positions from one side to another of the plane
comprising the three allylic carbon atoms:

111
Just as alkene complexes show similarity to carbonyls, the delocalized
allylic system CH2-CH-CH2 acting as a formal three – electron donor can be
linked to NO ligands in metal nitrosyl derivatives. These allylic derivatives
have also been visualized as a sort of halfsandwich, i.e., intermediate between
alkene and the sandwich compounds.

3.5.1 Methods of Preparation

Several types of allylic 3 – complexes have been prepared. Some of


them are monoleptic, M(allyl)n, and some are heteroleptic, M(allyl)n-a Xa:

1. Reaction of carbonyl complex with allylhalide:

(a) Na [Mn (CO) 5 ]  CH 2  CH  CH 2  Br  (CO) 5 Mn (   C3 H 5 )  Na Br

(b) (OC) 3 Mn (n  CH 2  CH  CH 2 )  (OC) 4 Mn( 3  C3 H 5 )  CO

2. From Grignard's reagent.

NiCl 2  2CH 2  CHCH 2 MgCl  Ni (n 3  C3 H 5 ) 2  2Mg Cl 2

Other transition metals like Ti, Zr, Hf, Th, V, Nb, Ta, Cr, Mo, W, Fe, Co
and Pt also follow this reaction. In some cases (e.g. Ni(II) and Pd (II)) this
reaction takes place in equimolar ratio and the product is M(3-allyl)x.

112
3. Protonation of complexes (e.g. tetrahapto 1-3 Butadiene):

3.5.2. Bonding and structure


The bonding of the allylic group to the metal is believed to be similar to
that of metal-alkene as explained on Dewar-Chatt-Duncanson model. For
example, the allylic group donates its  electrons to metal atom forming a-
type bond and accepts electrons into its antibonding *-molecular orbitals in a
-type bond. These allylic complexes, therefore, involve a three electron
delocalized allylic system. H2C = CH – CH2, as illustrated in Figure 3.9. Then
3- allyl group is in general symmetrically displaced around the transition
metal.
The 3-allyl group forms two metal donor bonds (one  and the other )
and one metal to ligand d-p bond. These three ligand molecular orbitals are
obtained by linear combination of p-orbitals on three allylic carbon atoms. (Fig.
3.9)
L-M electron donor bonds are formed by overlapping of metal s, d z2 and
pz orbitals with 2. After this M–L back bodning takes place, when metal dxz
orbital overlaps with 3. The degree of participation of these orbitals in bonding
depends upon their relative energies, radial diffuseness and orbital overlapping
magnitudes.

113
114
Z

Fig. 3.9

(b) -allyl M.O. and metal orbitals of corresponding symmetry


The structures of allyl-complexes have been established using x-ray and
n-diffraction methods and follow EA N-rule :

In structure (I) allyl radical is monohapto ligand :

Structure (I)
In Mn(CO)4 CH2 CH = CH2 (Structure II) it is trihapto ligand :

Structure (II)

115
In, trihapto complexes, e.g. Bis(3-allyl) nickel (structure III), the
terminal two carbon atoms of allyl group are at distance of 202.9 pm from the
metal atom and the central carbon atom is at the distance 198.0 pm. The C-C-C-
bond angle is 120.50 and the average C-C distance is 141.6 pm. Hence the
terminal carbon atoms are sufficiently bent, resulting in good -overlapping.
The C-C distance is in accordance with -conjugated system. Anti (trans from
meso) are bent away from metal and syn (cis from meso) are bent towards
metal atom.

in these complexes, due to position of carbon atom with respect to other


ligands, geometrical isomers are also known, e.g., Ru(3 – C3 H5)
(3 – C4 H7) CO gives both exo- and endo isomers (structure IV)

Structure IV

116
Other example include Mo and Cr complexes (Structure V and VI) :

Structure V

Infrared spectral studies. Some of the characteristic features of the


infrared spectra of 3-metal-allyl complexes of the type, <-M->, as revealed by
a study of Ni(II), Pd(II) and other metal derivatives can be summarized as
below: (a) the presence of a medium intensity C=C antisymmetric stretching
frequency near 1460cm-1, which is expected for a conjugated double-bond
system, (b) the occurrence of a symmetric C=C stretching vibration at 1020 cm-
1
, which is forbidden in ethylene complexes and shows that the bonding is not
of  or -2 type: and (c) the appearance of a strong C-H stretching vibration at
an exceptionally low position (2850 cm ) in some allylic complexes.
One of the important applications of i.r. spectroscopy to metal allylic
derivatives is the possibility of distinguishing between n1 and n3 type
bonding, by the appearance or absence, respectively of a bond just above

117
1600cm-1, The conversion of a 1-bonded allyl group into a -arrangement is
of greater interest from a mechanistic view point and has been more generally
studied in detail by n.m.r. technique. An example of such a rearrangement
which has been followed by i.r. and Hn.m.r. spectroscopy is illustrated below:
(Fig. 3.10.)

3.5.3. Chemical Properties

The important reactions of 3-allyl complexes are (a) Insertion, (b) Metal
exchange, (c) Halide exchange, (d) Displacement and (e) Nucleopuilic reactions
:
(a) Insertion reaction :
Cl

2[ Pt ( PPh3 ) 2 (  C 3 H 5 )] Cl  2CO  ( Ph3 P) 2 Pt
3   CHCl3


COCH  CH CH 3 (Cis and trans)

118
(b) Metal exchange reaction :

[{Pd X ( 3  C3 H5 )}2 ]  2Hg  2 Pd  Hg ( 3  C3 H5 )  Hg X 2

[{Pd X ( 3  C3 H5 )}2 ] [Co(CO)4 ] [Co (CO)2 ( 3  C3 H5 )] Co(CO)2 ( PPh3 ) ( 3  C3 H5 )


PPh 3

(c) Exchange reaction :

Pt ( 3  2  Me C3 H 4 )2  2E Ph3  Pt ( EPh3 )2 (1  C3 H5 ) ( 5  C5 H5 )

Cr ( 3  C3 H5 )3  6 PF3 Cr ( PF3 )6

Co (CO)3 ( 3  C3 H5 )  NO  Co (CO)3 ( NO)

(d) Halide Exchange

[{Pd (  x) ( 3  C3 H5 )}2 ]  2 Tl  C5 H5  2 Pd ( 3  C3 H5 )( 3  C3 H5 )  TIX

(e) Nucleophilic affack

(i) on metal :

(ii) On ferminal C-atom of allyl group :

119
CHECK YOUR PROGRESS -2

Note : (1) Write your answers in open space given below.

(2) Compare your answers with those given at the end of the unit.

(a) (i) The ................... structure of allyl group show that it is .................
electron donor, i.e. ........................ ligand or ................ electron
donor ...................... ligand in its behaviour.

(ii) The position of allylic derivatives may be considered in between


.................... and ................... compounds.

(b) (i) In LM dative bond are formed as a result of overlapping of


metal............., ................ and ................... orbitals with ................,
and ............... with metal ................. and .................... orbitals.

(ii) In trihapto complexes because of C-C-C bond angle being 120.50


and average distance 198 pm, the terminal ............ atoms are
....................., so that effective .................. may takes places.

(iii)The assymetric V(C=C) frequency is obtained near .............. Cm-1,


while V(C=C) symmetric frequency is obtained near ........... Cm-1.

3.4. LET US SUM UP

After going through this unit, you must have achieved the objectives
stated earlier in this unit. Let us recall what we have discussed so far :

 The alkene-metal bond involves both  donor and -acceptor linkage,


this is similar to that in metal carbonyls.

120
 Only the later transition metals, especially in their lower oxidation states
are known to form complexes and govern EAN-rule.

 First ethylene complex was Zeise salt, K[Pt(GH4)Cl3] prepared by the


action of ethylene with K2PtCl4.

 Alkeye complexes of transition metals are generally heteroleptic in


nature.

 The methods of preparation of alkene complexes involve (i) Reaction of


metal chloride or carbonyl with alkene, (ii) Displacement of hydride ion
from coordinated alkyl Ligand, (iii) Reductive alkenation, etc.

 The description of bonding in terms of a ,  scheme was suggested by


Dewar, Chatt and Duncanson (1953).

 Alkene ligands are dihapto two electron donor. Its filled -orbital,
donates electron pair to vacant orbital of metal to form LM -bond;
and the filled metal orbital donates electron pair to antibonding * orbital
to form ML -bond.

 Due to both  and -back donation V(C=C) stretching lower by 50-160


Cm-1.

 NMR studies indicate alkenes are generally non-rigidly bonded to


transition metals and these complexes are, therefore, often fluxional in
nature.

 The nucleophilic reagents react with these complexes to (i) replace


alkene or (ii) other ligands or (iii) attack on carbon atom of alkene.

121
 The homogeneous catalysed reactions are of industrial importance, these
include : (i) hydrogen, (ii) hydrosilylation, (iii) attack on carbon atom of
alkene.

 The homogeneous catalysed reactions are of industrial importance, these


include : (i) hydrogenation, (ii) hydrosilylation, (iii) Carboxylation, (vi)
hydroformylation, (v) Oligomerisation, (vi) Isomerisation and (vii)
Dismutation.

 Chemistry of alkyne complexes is quite complex, compare, to that of


alkene complex. The simplest alkyne complexes are analogous to alkene
complexes, e.g. L2Pt(RC  CR).

 In alkynes, two -bonds are perpendicular to each other, hence they can
not work as bidentate ligands. However in binuclear complex it can link
with two metals forming a bridge.

 The general methods of preparation of these complexes involve


displacement of ligands like carbonyl from metal complexes.

 Analogous to alkene, in alkyne also the bonding is shown by Dewar-


Chatt-Duncanson scheme, in which alkyne molecule behaves both as -
acceptor and -donor.

 According to Dewar-Chatt-Duncanson scheme -boding (Analogous to


alken complex) make CC bond weak, hence V(CC) frequency is
lowered  150 cm-1, compared to free acetylene.

 The principal reactions of alkyne complexes are : (i) Displacement

122
reactions, (ii) reaction with nucleophilic reagents and (iii) electrophilic
reactions. These reactions are used in organic synthesis.

 In 3-complexes, the simplest ligand is allyl group, C3H5. This forms -


bond with transition metal using its conjugated system.

 This can behave both as a monohapto and trihapto forms. Most general
form is trihapto. In it carbon-carbon distances are equal, which indicate
mobility of electrons in three -orbitals.

 3-allyl complexes are givne by d1-d8 transition metals in their lower


oxidation states.

 The most important method of synthesis of 3-allyl complex is reaction


of allyl halide with carbonyl complex.

 These complexes follow 18 electron (EAN) rule.

 During formation of -bond, allylic group donates its -electrons to


metal atom and during formation of -bond it accepts electrons from
metal into its antibonding * molecular orbital.

 In trihapto complex, the terminal two carbon atoms of allyl group are at a
distance of 202.9 pm from metal atom and the central atom is at a
distance of 198.0 pm and the C-C-C- bond angle is 120.50 and the
average distance is 141-6 pm. As a result terminal carbon atoms are bent
considerably, resulting in effective -overlapping.

 3-allyl complexes give following reactions :


(i) insertion, (ii) Metal-exchange, (iii) Halide exchange, (iv)

123
Displacement and (v) Nucleophilic reactions.
These reactions are of great importance in organic synthesis.

3.7. CHECK YOUR PROGRESS : THE KEY

1.(a) (i) 2-dihapto


3-trihapto

(ii) Zeise salt, K[Pt(C2H5)Cl3]

(iii) dsp2
Vacant
Filled
Bonding-
Vacant antibonding *
filled –d-

(b) (i) Fe3(CO)9 (CPh - CPh)

(ii) alkene
Dewar Chatt Duncanson scheme

(iii) -donor
-acceptor both

(iv) Cis
trans
2(a) (i) Resonance
One
Monohapto

124
three
trihapto

(ii) alkene
sandwich

(b) (i) s, dz2 and pz

1

2
Py an dyz

(ii) Carbon
sufficiently bent

-overlapping

(iii) 1460 cm-1


1020 cm-1

125
M.SC. (FINAL) CHEMISTRY

PAPER –IV : ORGANOTRANSITION METAL CHEMISTRY

BLOCK-II

Unit -4 : Transition Metal p . Complexes - II

Unit-5 : Transition Metal Compounds with Bonds to


Hydrogen.

Unit-6 : Homogenous Catalysis - I

Author – Dr. Purushottam B. Chakrawarti


Editor – Dr. Anuradha Mishra

126
M.Sc (Final) CHEMISTRY
Paper-4: ORGANOTRANSIONAL METAL
Block-II : Synthesis
This block includes three units, unit 4, 5 and 6.

Unit-4: Transition Metal  Complexes-II, records the nature, bonding


and structures of transition metal complexes of 4 to 6-hepto.
ligands (Butadiene, cyclobutadiene, cyclopentadiene and arenes).
Their applications. in organic synthesis is also discussed.

Unit-5: Transition metal compounds with bonds to hydrogen, discusses


nature and bonding in transition metal hydrides and different
transition metal complexes containing metal hydrogen bond (eg.
carbonyl hydrides, t. phosphines and arsines hydrides,  -
cyclopentadienyl hydrides and cyanide hydrides). In the end of the
unit, applications of these complexes in organic synthesis is also
discussed.

Unit-6: Homogeneous Catalysis-I, describes various stoichiometric


reactions of transition metal organometallic compounds useful in
organic synthesis, these include metal alkylidene, alkylidynes,
carbenes, alkenes, alkynes, allyls, dienes, cyclopentadienyl and
arene complexes which are important in homogeneous catalysis.

127
UNIT – 4 TRANSITION METAL  - COMPLEXES – II

Structures
4.1 Introduction
4.2 Objectives
4.3 4 Complexes

4.4 Butadiene complexes


4.4.1 Methods of preparation
4.4.2 Bonding and structure
4.4.3 Reactions

4.5 Cyclobutadiene complexes


4.5.1 Methods of Preparation
4.5.2 Bonding and Structure
4.5.3 Reactions

4.6 Cyclo-Octatetraene Complexes

4.7 Cyclo Pentadienyl Organometallic Complexes: Metallocanes


4.7.1 Cyclopentadienyl, 5 – Complexes:
4.7.2 Characteristic Properties

4.8 Arene – Organometallic Complexes : 6-complexes


4.8.1 Methods of Preparation
4.8.2 Bonding and Structure
4.8.3 Characteristic Properties
4.9 Let us Sum up
4.10 Check your progress : The key

128
4.1 INTRODUCTION

The chemistry of organometallic derivatives of transition metals shows


many similarities to that of the carbonyls and their derivatives. However,
whereas in the carbonyls the carbon atom uses its lone pair of electrons to
provide the primary bond, in the case of complexes of transition metals
with systems capable of providing more than two electrons the 
electrons themselves are involved in the primary bond formation. In
contrast to the carbonyls, in which the metal atom is in the nodal plane of
the  electrons, bonding in the olefin and other complexes (which we
may take as the simplest example) is perpendicular to the nodal plane.
The primary bonding is reinforced, as in the carbonyls, by back –
donation from a filled transition metal t2g orbital to a * orbital of the
ligand.

However, some of the complexes of dienes, dienyl complexes


show fluxional behavior.

In this unit we shall discuss the nature of different complexes of


transition metals formed by 4 to 6 hapto ligands. Their applications in
organic systhens will also be discussed.

4.2 OBJECTIVES

The main aim of this unit is to discuss nature and bonding of transition
metal complexes of 4 to 6 hepto ligands. After going through this unit you
should be able to:

 describe the various methods of their systhesis,

129
 discuss the nature of bonding in these complexes,

 based on the nature of bonding, discuss their structures, and

 understand their applications in organic systhesis in the light of their


principal reactions.

4.3 4 COMPLEXES

Under this heading we shall consider briefly complexes of acctyene


dienes and cyclic dienes. Since there are two  bonds in acetylene it should be
feasible to complex a metal atom with each of them.

Diphenylacetylene, for example, displaces the bridging carbonyls from


Co2 (CO)8 when these substance are heated together in benzene. e.g.

Benzene
(C6H5)2 + Co2 (CO)8
Heat

Benzene
C2F4 + Co2 (CO)8
Heat

130
4.4 BUTADIENE COMPLEXES

Butadiene iron tricarbonyl was first made in 1930, by the action of


butadiene on iron pentacarbonyl under pressure. The product is a yellow –
brown oil which is soluble in most organic compounds and is slowly oxidized
by air. Different transition metals (eg. Ti, V, Nb, Cr, Mo, W, Fe, Co, Ni, Ru,
Rh, Pd, Ir and Pt) form 4 – Complexes. These follow EAN rule.

4.4.1: Methods of Preparation

Butadiene complexes are generally prepared by following two methods:

1. Reaction of butadiene with metal carbonyl (By photochemical, thermal or


chemical reactions):

2. nkc
(i) Fe (CO)  CH  CH  CH  CH  Fe(CO) ( 3  C H )  2CO
5 2 2 3 4 6
3. (ii) Fe (CO)  CH  CH  CH  CH 
UV
Fe(CO) ( 4  C H )  4CO
5 2 2 4 62
4.

(v) Mo (CO)  CH  CH  Ch  CH  Mo (CO) (η 4  C H )  2CO


6 2 2 4 4 6

(vi) Mo (CO)  2CH  CH  CH  CH  Mo (CO) (η 4  C H )  4CO


6 2 2 4 4 6 2

131
(vii) RhCl  CH  CH  CH  CH  RhCl (η 4  C H )  4CO
3 2 2 4 6 2

2. Synthesis with metal vapour:

(i)  Cr(CO) (η 4  C H )


Cr  CH  CH  CH  CH 4CO
2 2 4 4 6

(ii) M  3 CH  CH  CH  CH  M ( 4  C H )
2 2 4 6
(M = Mo, W)

4.4.2 Bonding and structure

The structure of the first transition metal butadiene complex is shown in


structure – III.

Structure-III : Fe(CO)3 (4 C4H6)

In the above structure the ligand is in the cis configuration, the plane of
four carbon atoms being nearly parallel to that of the carbonyl groups. The
metal atom is equidistant from each of the four carbon atoms in the diene and
the carbon – carbon bond lengths are all equal.

The bonding in 4 – butadiene transition metal complexes can be


described by constructing molecular orbitals of the diene system with the
appropriate combinations of the 4p orbitals, which are then used to combine

132
with the metal-based orbitals of suitable symmetry for donation and acceptance
of electron density.

The four pz atomic orbitals on the butadiene fragment can be combined


to give four group MOs as shown in Fig. 4.1. The orbitals of buta-1, 3-diene
and the appropriate metal orbitals having the same symmetry are in the same
rows. It is worthwhile to mention that the number of nodes is directly related to
the orbital energy. Thus in all cases, successively higher energy orbitals have
molecular orbital nodes symmetrically placed and increasing in number by one
in the order of decreasing stability.

Fig. 4.1. : Orbitals of butadiene used in bonding

133
Orbitals are important, then the geometry of butadiene moiety is pretty
well like.

The complex follow EAN rule:

Structure - IV

In an another complex, formed by the action of cyclopentadiene and iron


pentacarbonyl is shown in structure (V).

Structure-V
4.4.3 Reactions

The important reactions of butadiene are: 1. Substitution, 2. Nucleophilic


addition 3. Electrophilic addition and 4. Reactions of substituents in ligand.

1. Substitution Reactions:
In these reactions diene ligand is nucleophilically substituted.
Fe (4-C4H6) (CO)3 + 2PPh3  Fe (CO)3 (PPh3)2 + C4H6

134
2. Nucleophilic addition:
In these reactions due to nucleophilic reaction of H-, R-, CN-, MeO-, R3N
etc. (Nucleophilies) on carbon of oleffins, diene ligand or any other
ligand is displaced or addition on carbon taken place:

3. Electrophilic addition
In these reactions there is addition of proton or eliminatation of proton:

4. Reaction of substituent groups:

135
5. CYCLOBUTADIENE COMPLEXES

Although the possibility of formation of cyclobutadiene complexs had


been proposed on theoretical considerations by H.C. Longuet – Higgins and
L.E. Orgel as early as 1956, yet the free ligand has not been isolated (except as
a matrix-iso-lated species) and distinguished organic chemists have some –
times compared it to 'snark', an imaginary animal described by the famous
author Lewis Carroll.

Beginning (in 1959) with the first cyclobutadiene nickel complex,


[{NiCl(-Cl)(4-C4Me4)}2], a large number of complexes of transition metals
with such ligands are now known.

Cyclobutadiene nickel complex was prepared by the action


dichlorotetramethyl cyclobutadiene with Ni(CO)4. It was obtained as a polymer
in which chlorine atoms form bridges (Structure VI):

Structure - VI

136
4.5.1 Methods of Preparation
Many other cyclobutadiene complexes are now known, among them the
unsubstituted  - cyclobutadiene iron tricarbonyl prepared by the

Structure VII

reaction shown in structure-VII The palladium complex of tetraphenyl-


cyclobutadiene (which is analogous to the nickel complex mentioned above) is
readily obtained from diphenylacetylene and palladium (II) chloride. It reacts
with a wide range of metal carbonyls and -cyclopentadienyl complexes,
transferring one C4Ph4 group to another metal; for example,

[C4Ph4PdCl2]2 + (-C5H5)2 Co  (C4Ph4) Co (-C5H5)

Other butadiene complexes are prepared by the reactions of acetylene, or


cyclobutadiene derivatives or metalocyclopentadiene etc:

137
S.5.2 Bonding and structure

X-ray diffraction studies of complexes of methyl- and phenyl-substituted


cyclobutadienes show that the C4 ring is square-planar; the substituents are
slightly displaced out of the plane of the C4 ring on the side remote from the
metal atom.

however, it has been conclusively shown that on complexation with


transition metals, cyclobutadiene assumes a square configuration as illustrated
by the structure of the iron carbonyl complex structure VII.

Free cyclobutadiene molecules in their square planar form would


incorporate two electrons in 1 (Fig. 4.2(a)) and only one unpaired electron in
each of two (2 and 3) degenerate levels. In the alternative rectangular form of
cyclobutadiene, spin pairing (Fig. 4.2(b)) will effectively bring the orbitals in
the energy sequence shown in Fig. 4.2

138
(a) (b)

Fig. 4.2 Energy level diagram for a. square,


and b rectangular cyclobutadiene.

It may be reemphasized that complexation of cyclobutadiene with


transition metal would occur when both the metal and ligand have similar
energies along with matching signs of their wave functions. On complexation,
cyclobutadiene ligand automatically assumes a square planar shape structure
VII.

In the cyclobutadiene complexes, the electrons are accommodated in


molecular orbitals arising from 2 and 3 (Fig. 4.2), which retain ligand
character to a high degree. The four-membered ring ligated cyclobutadiene
should, therefore, be considered preferably as a six-electron aromatic system,
rather than as a two  - electron aromatic system. Thus, the overlaps between
metal and 2 as well as 3 orbitals contribute predominantly to the bonding in
the complex, as illustrated in Fig. 4.3

139
Fig. 4.3 : Butadiene – Metal - Bonding

4.5.3 Reactions
Cyclobutadiene appears to be too labile for independent existence, thus,
when released from their captive traps (combinations with transition metals),
these highly reactive molecules rapidly decompose, dimerize or isomerize or
react with suitable organic substrates to generate new novel organic products:

140
Other reactions are decomposition and dimerisation, or isomerisation
giving novel products:

141
Dewar Benzene

4.6 CYCLOOCTATETRAENE COMPLEXES

Cyclo-Octatetraene is not aromatic like cyclobutadiene molecule. It has


alternative bond lengths and has shape similar to a tub. In its structure due to
presence of two pairs of double bonds, it forms 4 – complexes with many
metals. Amongst these Ru, Co, and Mo complexes cyclo octatetraene molecule
links with metal atom donating four electrons (two pairs):

Structure IX

142
Or

Structure X

Similarly the structures of cobalt (structure XI) and molybdenum


complexes (Structure XII) may be given as follows:

Structure XI
Cyclo Octatetraene Cyclopentadinyl Cobalt (II)

Structure XII
Cyclo Octatetraene Tetracarbonyl Molybdenum

143
CHECK YOUR PROGRESS – 1

Notes: 1. Write your answers in the space given below.

2. Compare your answers with those given at the end of the unit.

a. 1. Simplest 4 – complex is:


...............................................................

2. General methods for preparation of butadiene complexes are:

(x) ...............................................................

(y) ...............................................................

3. During formation of diene complexes, diene system using its ...............


orbitals and making appropriate combinations forms .........................,
which combine with metal orbitals of .......................... to give complex
compound.

b. 1. Cyclo Octatetraene forms complexes generally with ....................,......


....................... and ...................... metals. In these complexes cyclo
Octatetraene combines with ....................... atom, giving ..................
(................ pairs).

2. In Ru3 (Cy Oct.)2 (CO)4 structure, the apex Ru atom receives ................
electrons from ........................ molecules, while each of the base Ru atom
receives ......................... electrons from ..................... molecule.

144
4.7 CYCLOPENTADIENYL, 5 – COMPLEXES

Metallocenes:

Ligands formally contributing five electrons when bonded to a transition


metal are called dienyl ligands; much the most important of them is the
cyclopentadienyl group, C5H5. Ferrocene, Fe (5-C5H5)2, and other
'Metallocenes' are the compounds in which metal atom is sandwiched between
two cyclopentadienyl or other carbocyclic rings. In 1950 Ferrocene was
discovered, it was the first metallocene prepared. The name was assigned due to
their properties, analogous to aromatic molecules. Metallocenes with different
carbocyclic rings have been prepared.

4.7.1 5-Cyclopentadienyl Complexes:

The -cyclopentadienyl metal bond in many complexes has a high kinetic


stability towards thermal decomposition and oxidation, and very large numbers
of -cyclopentadienyl derivatives are known. Alone among transition metal
complexes of this kind, the parent bis– (-cyclopentadienyl) metal complexes
are known by trivial names analogous to that of ferrocene, ( - C5H5)2 Fe, the
first of these compounds to be prepared.

145
All metals of the first transition series from titanium to nickel inclusive
are now known to form neutral bis- (-cyclopentadienyl) complexes, and those
of vanadium, chromium cobalt and nickel are isomorphous with ferrocene. Bis
(-cyclopentadienyl) derivatives of zirconium, technetium, ruthenium, osmium,
rhodium and iridium have been prepared, those of ruthenium and osmium have
been shown to have a structure similar to that of ferrocene, but with the rings in
the eclipsed conformation. They are less stable than ferrocene. The order of
their reactivity being:

CP2Fe < Cp2 Ni < CP2 Co < Cp2 V < Cp2 Cr < Cp2 Ti

Methods of Preparation:

The first two preparations of ferrocene were both accidental, the


compound being obtained by the interaction of cyclopentadienyl magnesium
iodide and iron (III) chloride, and by the action of cyclo-pentadiene on reduced
iron at 300º.

Fe3 CpMgBr
  Fe 2  Fe (η5C H )
2CpMgBr
5 5 2

Ferrocene forms orange crystals which sublime at 100º and are insoluble
in water but soluble in many organic solvents. It undergoes many of the
conventional electrophilic substitution reactions of organic chemistry, notably
acylation, alkylation, halogenation and metallation; but it is more resistant than
benzene to hydrogenation.

The general method for the preparation of these compounds is by the


action of freshly prepared sodium cyclopentadienide on a halide or other
soluble salt in tetrahydrofuran, 1, 2-dimethoxyethane or other ethers.

146
Alternatively, the action of cyclopentadiene on a metal halide in a basic solvent
may be used; for example,

MnX2 + 2Na C5H5 M (5-C5H5)2 + 2 Nax

The complexes of other metals (Cr, Fe, Co, Ni) are also prepared using
similar method. However, now a days in place of sodium cyclopentadinide,
thallium cyclopentadinide is preferred. Because sodium is a strong
electropositive, hence the product is reduced to give hydride complex. The use
of thallium salt considerably reduces this possibility.
THF
  5
Re Cl2  Na C5 H  ReH ( -C5H5)2
5

(Re flex )

The other important methods of preparation are:

(a) Reaction of metal halide with cyclopentadiene in presence of a base


(pyridine, diethylamine etc):

MCl2+2C5H6+2NH(C2H5)2(5-C2H5)2 MNH2+Cl;(M=Fe,Co,Ni)

(b) Reaction of cyclopentadiene with metal or metal carbonyl:

2C5H6+Fe (atom)Fe(5-C2H5)2 + H2
Fe (CO)5+C10 H12 Fe(5-C2H5)2 + (CO)3

Bonding and structures


The structure of ferrocene in the solid state is shown by X-ray diffraction
to be a sandwich in which the two cyclopentadienyl groups are staggered with
respect to one another; an electron diffraction study of the vapour shows that in
this phase the rings are eclipsed. All C – C distances in the ring are 1.40 + 0.02

147
A, almost exactly the same as in benzene. The inter – ring distances is 3.22 A,
and the iron-carbon distance 2.04 A. The compound is diamagnetic.

X-ray studies of solid ferroene indicate its sandwich structure. The two
cyclpentadienyl group are placed in this structure in staggered configuration.
However electron diffraction studies in vapour state show them in eclipsed
form.

With reference to ferrous iron, structure of ferrocene is pentagonal


antiprismatic. In this coordination polyhedron structure one ring of five
membered carbon atoms i.e.  - cyclopertadienyl is above, and the other ring is
below Fe++ ion, forming a pentagonal prism. These rings are in staggered or
eclipsed forms.

The pentagonal ring of Cp (C5H5), analogous to hexagonal ring of


benzene, is obtained by Sp2 – hybridisation of carbon atoms. Two \Sp2- hybrid
of two carbon atoms overlap, resulting in a pentagonal ring as shown in Fig.
4.5.

Fig. 4.5

148
Thus skeleton is obtained. Each sp2- hybrid has single electron. In
addition, each pz orbital of each carbon atom has one electron, which is used
for formation of mobile (delocalized) -bond. In this way five electrons from
five carbon atoms and an additional electron (obtained due to Cp - formation)
give total six electrons, which are placed in three of the five -bonding orbitals
(as electron pair); while remaining two -bonding molecular orbitals remain
vacant. During combination with central Fe (II) [d2 sp3- hybridised], each Cp
coordinates giving three electron pairs (Fig. 4.6).

Fig. 4.5. Ferrcene formation

Now the filled orbitals (t2g) of Fe (II), form back  - bond with vacant
antibonding orbitals (* MoOs) of CP-. In this way each Cp- links as  donor
and  - acceptor, with Fe (II). Thus sandwich complex is formed (Fig. 4.7).

Eclipsed Fe Fe Staggered

149
150
Fig. 4.7 Ligand group orbitals and matching atomic orbitals
of iron for ferrocene.

151
On molecular orbitals theory, five p orbitals (one on each carbon atom)
are available for orbital formation, linear combinations of which can give rise to
three bonding and two antibonding molecular orbitals. The most strongly
bonding overlap (i.e. all the wave functions on one side of the ring have the
same sign) and this is designated as 'A'. At slightly higher energy there is a
doubly degenerate set of molecular orbitals (E1) each of which has one nodal
plane. This is followed by another doubly degenerate set of molecular orbitals
with two nodal planes and yet higher energy. A schematic representation of the
 - molecular orbitals of cyclopentadienide anion is given in Fig. 4.8 with their
energy increasing from bottom to top.
To construct the ten ligand group orbitals of ferrocene from two
cyclopentadienide anion, the five group molecular orbitals of one
cyclopentadienide anion are combined in pairs with a similar set from the
second C5H5 in symmetric and antisymmetric and matching atomic orbitals of
iron for ferrocene are shown in Fig. 4.8(a). In an LCAO molecular orbital
treatment of bonding in metallocenes, of the atomic

Fig. 4.8 The  molecular orbitals formed from the set of five porbitals of
the cyclopentadienide anion C5H5

152
153
Fig. 4.8 (b)

154
orbitals of the metal ion are grouped by symmetry. Thus for ferrocene, the
metal orbitals are designated as: d, dz2 (a1), pz (a2u); dxz, dxz dyz (e1g); px, py (e1u);
dxy, dx2–y2 (e2g) where 'a' and 'e' indicate nondegenerate and degenerate where g
and u represent symmetric and antisymmetric nature of the orbitals.

If both rings have the positive lobes of their lowest energy orbitals on the
sides nearer to the metal, then s and dx2, orbitals would have the correct
symmetry; if one of the rings has the positive lobe nearer to the metal and for
the other ring, the negative lobe is nearer to the metal, the pz orbitals has the
correct symmetry.

Provided that the energies of the two component sets are not too far apart,
each of the combinations shows in Fig. 4.8 (b) represents a bonding MO of the
molecule. Although for simplicity, these are not shown, yet there are an equal
number of antibonding combinations. It is quite apparent that no metal orbitals
of appropriate symmetry are available to combine with the degenerate ligand
sets labelled as e2u.

Interactions with the metal orbitals having appropriate symmetry for


overlap, lead to metal – ring  - bonding through 19  - bonding through 2
and 3, and  - bonding through 4 and 5. It may be noted that the correct
symmetry will not necessarily lead to appreciable bonding interaction; in fact,
for this purpose it is also necessary that the orbitals involved should be of
similar energies.

The simplified molecular orbital energy – level diagram that results from
the above considerations for ferrocene is shown in Fig. 4.9

155
(Ligand orbitals) (Metallocene orbitals) (Metal orbitals)

A perusal of the MO diagram for ferrocene indicates that ligand group


orbitals can be categorized in three sets: a filled pair of a1g and a2u symmetry; a

156
higher energy filled set of e1g and e1u symmetry; and even a higher energy
unfilled set of e2g and e2u symmetry. It can be noticed that the metal dxz and dyz
orbitals have been found to interact more effectively with the cyclopentadienyl
ligand group orbitals than the metal s (a1g); px, py (e1u); and pz (a2u) orbitals.
These bonds are believed to provide most of the stabilization that holds the
ferrocene molecule together. The antibonding e2g ligand orbitals interact with
the metal 3dx2-y2 and 3dxy orbitals producing slightly bonding molecular
orbitals which comprise mostly of metal orbitals. Based on the above simple
molecular orbitals picture, it is not surprising that the ferrocene in which all the
nine molecular orbitals of the lowest energy are occupied by electrons, is the
most stable metallocene.

If in ferrocene only all the bonding and non bonding orbitals are filled
(i.e. nonbonding orbitals are not filled) then nine electron pairs (total 18
electrons) will be necessary. This confirms 18 electron – rule. (But this is not
universal see table 4.1)
Table 4.1.
Compound Colour Unpaired Electronic
Electrons Configuration
Cp2V Pink 3 e22g a11g
Cp2Cr Red 2 e23g a11g
Cp2Mn Amber 5 e22g a11g e12g
Cp2Fe Orange 0 e24g a12g
Cp2Co Pink 1 e24g a12g e11g
Cp2Ni Green 2 e24g a12g e12g

The important information regarding bonding in metallocene is obtained


from IR spectroscopy. The  bonding bands in metallocene are given as follows

157
(Reference: Ferrocene):
v (CH) v (C=C)  (CH) π (CH) Unsymmetrical M–R
Bent Stretching
3086 1408 1001 854 490 478
2909 1104 814

4.7.2 Characteristic Properties


On the basis of structures 5- cyclopentadinyl complexes are classified in
to three groups:

(i) M(Cp)2, symmetrical "sandwich" type derivatives represented by Fe(5 –


C5H5)2 (ferrocene), Co (5 – C5H5)2 Mn (5 – C5H5)2 etc., often called
'metallocenes' (see Figure 4.7(a))

(ii) (Cp)2 MLx, "bent metallocene" derivatives, in which the plane of two
cyclopentadienyl rings are at an angle and L represents some other ligand
such as hydride, alkyl(aryl), halide, alkene, carbon monoxide or even 1
– cyclopentadienyl groups and 'x' may have values generally from one to
three (Fig. 4.10).

Important examples are Cp2 ReH, Cp2 Ti Cl2 and Cp2 Ta H3.

Fig. 4.10

(iii) (Cp)3 M2, Triple deckers, e.g. Cp3 Ni2. In this complex there is layered

158
structure involving cyclo-pentadienyl rings and nickel atoms (Fig. 4.11)

Fig. 4.11

(iv) (Cp) MLx, 'half-sandwich" compounds, where L = ligands like H halide,


CO, PR3 etc. and x may values from one to four. Most important
compounds in this category are cyclopentadinyl carbony complexes, eg.

[(5-C5H5) V (CO)4], [(5-C5H5) Cr (CO)3]2, [(5-C5H5) Mn (CO)3],


[(5-C5H5) Fe (CO)2]2, [(5-C5H5) Co (CO)2] and[(5-C5H5) Ni
(CO)2]

An important fact, about these compounds is that the elements with even
number of atomic number form dimer, while the elements with odd number of
atomic number (V, Mn and Co) form monomer. This behaviour is quite
opposite to that of normal carbonyls. All these compounds follow EAN rule.
(Fig. 4.12):

159
Fig. 4.12 Cyclopentadinyl Carbonyl Complex

 - cyclopentadienyl carbonyl complexes are generally prepared by the


action of cyclopentadiene on metal carbonyls or action of carbon monoxide on
cyclopentadienyl complexes:
2C5H6 + Co2 (CO)8 2(C5H5) Co (CO)2 + 4 CO + H2
Nickel complex is prepared by direct ligand substitution reaction:
( C5H5) Ni + Ni (CO)4 [ (C5H5) Ni (CO)2]2
Beryllium and magnesium complexes have special importance with
reference to ionic bonding, opposite to covalent bonding. Although, magnosine,
Cp2Mg, has structure similar to ferrocene, but it is considered mainly ionic.
According to H' – NMR, it is fluxional molecule, while x-ray and electron
diffraction studies show it a slipped sandwich complex. In which one Cp ring
is pentahapto and the other is  - or probably  - bonded. (Fig. 4.13)

Fig. 4.13

160
Theoretically metallocene should give aromatic reactions. But these are
generally not stable in these reactions. As compared to benzene, metallocene
are more reactive with electrophilic reagents.

Cyclopentadienyl complexes are covalent compounds. These are stable


not only for oxidation, but also thermodynamically. Some specific reactions are
given below:

1. Aromatic Properties

161
2. Protonation of metal
(i) Fe (5-C5H5)2 H+ [FeH(5-C5H5)]

(ii) ReH (5-C5H5)2 H+ [ReH2(5-C5H5)]+

(iii) MoH2 (5-C5H5)2 H+ [MoH3 (5-C5H5)2]+

3. In these (5 – C5H5) is transfered to other metal


(i) M (5-C5H5)2 + Fe Cl2  Fe (5-C5H5)] + MCl2 (M=Cr, Mo, V, Mn)

(ii) Ni (5-C5H5)2 + Fe (CO)5  [(5-C5H5) Ni (CO)2 Fe (CO)(5-C5H5) +


2CO

(iii) Ni (5-C5H5)2 + Ni (CO)4 2[Ni (CO)(5-C5H5)2] + 2CO

5. Reduction Reaction
Metal atom or / and cyclopentadienyl group is reduced
(i) Co+ (5-C5H5)2 + Na BH4 Co (5C5H5) (4-C4H6)
C2H2NH2
(ii) Fe (5-C5H5)2 + Li Fe + 2 C5H5-

5. Addition reaction

162
4.8 ARENE ORGANOMETALLIC COMPLEXES

The ligands in this group are benzene and substituted benzenes,


particularly mesitylene and hexamethylbenzene (arenes), and trienes, of which
cycloheptatriene has been most investigated.

The simplest and the most common six electron donor arene ligand is, of
course, benzene, but other arene moieties can also function in the same fashion.
Although the first 6-arene metal complexes were reported by Hein as early as
1919, yet it took almost 35 years for their definitive characterization by the
synthesis of the prototypical "sandwich" compound Cr (6 – C6H6)2 by E.O.
Fischer in 1955. Since then the chemistry of arene metal complexes has
undergone remarkable transformations leading to the synthesis of 6 – arene
complexes of almost all transition metals (d2 – d8)

4.8.1 Methods of Preparation

Neutral bis-arene complexes of vanadium, chromium, molybednum,


tungsten, iron and cobalt have so far been prepared. Dibenzene chromium, the
first arene complex to be correctly identified, is best made by the action of

163
benzene on chromium (III) chloride in the presence of aluminium and
aluminium chloride, the resulting cation [(-C6H6)2 Cr]+ being reduced to the
neutral complex by dithionite or allowed to disporportionate in the presence of
aqueous alkali:

The vanadium, molybdenum and tungsten compounds are obtained by


analogous methods. Alkyl substitution in the ring substantially increases
stability, and for iron and cobalt only hexamethylbenzene derivatives have been
prepared; conversion of the cations [(-C6Me6)2 Fe]2+ and [(-C6Me6)2 Co]+ to
the neutral complexes requires powerful reducing agents such as sodium in
liquid ammonia.

The other methods of preparation are:

(i) Displacement of weakly coordinated :

M (CO) 6  Arene 


hv
M (CO) 3 ( 6 Arene)  3CO

(M= Cr, Mo, W)

(ii) Generation of a highly unsaturated metal by reducing a higher


oxidation state in the presence of an arene, e.g.,


3Crl3  AlCl 3  6C6 H 6  2 Al 3 Cr ( 6  C6 H 6 ) 2  AlCl 

4

 Cr ( 6C6 H 6 ) 2
Na2 S2O4 50 C
0

164
(iii) Metal vapour synthesis. This technique has provided a synthetic route for
a very wide range of bis (arene) metal  - complexes, many of which
were inacessible by conventional techniques:
(i ) cocondenses,77 K
MnCl 2  arene      M ( 6  arene) 2
(ii ) warm

(M = Ti, V, Nb, Cr, Mo, W, Fe, etc; arene = C6H6, C6H5Me,


Me3C6H3, etc.)

(iv) Cyclization of alkynes, e.g.,


(i ) MgBr ( Ar )
Mncl 2  MeC  CMe      Mn( 6  C 6 Me6 ) 2
(ii ) H 2 O

(v) Grignard method. Through the formation of a  - bonded derivatives e.g.,

4.8.2 Bonding and structure

The neutral complexes are crystalline solids which sablime in vacuo at


about 100ºC and are mostly thermally stable up to 200-300ºC. They are soluble
in organic solvents but not in water. In both the vapour and the solid, dibenzene
chromium is a sandwich molecule; all the C-C distances in the ring are 1.42 A
(slightly more than in benzene itself), and the Cr-C distances are 2.15 A. The
metal – ring bond energies in dibenzene chromium and dibenzene molybdenum
are approximately 170 and 210 KJ (40 and 50 kcal) respectively. (Fig. 4.14)

165
Cr

Fig. 4.14

According to V.B.T., structure of dibenzene chromium is octahedral due


to d2 sp3 hybridisation of chromium.

In molecular orbital description planar C6H6 molecule combines its six


p orbitals, in an analogous fashion to C5H5 group, to give six molecular
orbitals. Out of these three are bonding and remaining three are antibonding
molecular orbitals. Analogous to ferrocene, these six molecular orbitals of one
benzene, combine automatically with the set of other benzene and overlap with
metal orbitals of corresponding symmetry, resulting in the formation of sets of
bonding and antibonding molecular orbitals (Fig. 4.14). The symmetry of metal
orbitals are a1g (s, dz2), a2u (pz), e1u (px, py), e1g (dxz, dxy), e2g (dxy, dx2-y2).

A perusal of fig. 4.15 clearly indicates, 12 electrons (6 from each benzene


ring) fill six bonding molecular orbitals (a1g, a2u, e1g and e1u). Thus each benzene
ring behaves as a six electron donor. Further, six electrons of chromium (d 5 s1)
fill further three orbitals, which are mainly on the metal atom. The complex is
stabilized by back bonding. For this two eg. orbitals (dx2-y2 and dxy) overlap
with vacant antibonding orbitals of benzene ring.

166
Fig. 4.15 Molecular Orbital diagram of dibenzene chromium.

167
Characteristic Properties
These compounds resemble metallocenes in their solubility in organic
solvents and in volatility, but these are generally more reactive than their 5 –
C5H5 analogues and are thermally and aerially less stable. For example, Cr (6-
C6H6)2 undergoes facile oxidation to [Cr (6-C6H6)2]+. This ease of oxidation of
Cr (6-C6H6)2 is also reflected by its reaction with alkyl halides, generating
alkyl radicals which undergo usual disproportionate / addition reactions:

However, (6-arene) complexes do undergo substitution, addition,


metallation, mercuration, nitration, expansion, reactions in limited and specific
cases. There should be much less competitions for nucleophiles and therefore
nucleophilic substitution is enhanced compared with free arenes. Unlike the
cyclopentadienyl group, arene ligands are readily displaced from complexes by
other neutral ligands, such as carbon monoxide, phosphines, 2, 2' – bipyridyl,
etc. Some important reactions are as follows:

1. Arene displacement reaction


Cr( 6  C6 H6 )2  C6 H5 H3  3CO 
nkc
Cr(CO)3 ( 6  C6 H5CH3 )  C6 H6

1000 C
Mo( 6  C6 H 6 )3  6 PF3  Mo ( PF3 ) 6  2C6 H 6
600 Air

2. Reaction with arene ligand

Arene complexes give substitution and addition reactions with weak


nucleophilic reagents like H-, R-, MeO-, R3N etc.
( 6  C6 H 6 ) 2 Cr  MeO  ( 6  C6 H 6  OMe)  Cr ( 6  C6 H 6 )

( 6  C6 H 6 ) 2 Re   H   ( 6  C6 H 6 )  Cr ( 6  C6 H 7 )

168
lkbDyksgsDlsu
( 6  C6 H 6 ) 2 Cr   Li Bu   ( 6  C6 H 6  Li)  Cr  ( 6  C6 H 6  Li)
700 C

Due to metallation with lithium, the product can be used for many
organic synthesis:

3. Redistribution:
Cr ( 6  C6 H 6 ) 2  Cr (CO) 6  Cr (CO)3 ( 6  C6 H 6 )

4. Redox reaction:1
2 Cr ( 6  C6 H 6 )2  O2  2H 2O    2[Cr ( 6  C6 H 6 )2 ] OH 
Na2 S 2 O4

5. Friedel – Craft Acylation


CH 3COCl
(  C6 H 6 ) 2 M       ( 6  C6 H 6 )  M   ( 6  C6 H 5CH 3 )( M  Cr , Mn)
6

AlCl 3 rFkk ty vi?kVu

Amongst mixed complexes arene – carbonyl complexes are important.


These may be prepared by replacement of CO from metal carbonyls.
Cr (CO)6  C6 H 6  (C6 H 6 ) Cr (CO)3  3CO

These complexes are more reactive compared to corresponding bis


are3nes. They also follow. EAN rule (Fig. 4.16)

CR

C C C
O O O

Fig. 4.16

169
Check Your Progress – 2

Notes:1. Write your answers in the space given below.

2. Compare your answers with those given at the end of the unit.

(a) 1. In metallocenes metal atom is sandwiched in between ...............


........................................................ An important example is ferrocene,
formula.................................

2. Structure of ferrocene is .................................................. According to


................................. are in ................................. forms from one another.

3. In ferrocene, leaving ............................................................ orbitals, if all


................................. and ..................................... orbitals are filled, then
total ................................. electron pairs will be needed, which confirms
................................. electron rule.

4. An example of triple decker complex is .................................

(b) 1. The first 6- arene complex was ........................................... which was
synthesised by ................................. in..................................

2. According to molecular orbitals concept, Six .........................................


orbitals of planar C6H6, analogour to ................................. group combine
to give ................................. orbitals. Out of which .................................
are bonding and remaining ....................................................... orbitals are
...............................................................

3. According to V.B.T. structure of dibenzene chromium is


................................. due to ................................. hybridisation.

170
4.9 LET US SUM UP

After going through this unit, you would have achieved the objectives
stated earlier in this unit. Let us recall what we have discussed so far:

 Amongst 4-group of complexes, we can consider complexes of


acetylene, dienes and cyclodienes

 An important complex of this group is butadiene iron tricarbonyl, (C 4H6)


Fe (CO)3. This was prepared, for the first time, by the action of butadiene
and iron pentacarbonyl, in 1930.

 Two methods are generally used for synthesis of butadiene complexes:


1. Action of butadiene on metal carbonyls, and
2. Synthesis from metal vapour.

 In these complexes, diene system using its 4px orbitals hybridise


appropriately to give molecular orbitals, which combine with metal
orbitals of same symmetry to form the complex.

 In butadiene complex, the ligand is in cis – form and the layer of four
atoms, is parallel to three carbonyl groups. The metal atom is at
equidistance with the four atoms.

 The important reactions of butadiene complexes are : 1. Substitution, 2.


Nucleophilic addition, 3. Electrophilic addition and 4. Reactions of
ligand – substituents.

 Nickel complex of cyclobutadiene is in polymeric state. Its reactions


show aromatic character.

171
 Cyclooctatetraene is not aromatic analogous to cyclobutadiene. The
important 4-complexes with the ligand are Ru, Co and Mo – complexes.
In which it donates four electron to the metal atom.

 In Ru3 (Cy O.T.)2 (CO)4 molecule, the apex Ru atom receives 8 electrons
from two cyclo – octa tetraene molecules (of 4 electrons from each
molecule), while out the two base Ru atoms, each one gets four electrons
from one cyclooctatetraene molecule during the combination.

 Amongst 5- complexes, most important are ferrocene, Fe (5-C5H5)2 and


other metallocenes. In which metal atom is sandwiched between two
cyelopentadienyl rings.

The order of their reactivity is: CP2 Fe < Cp2Ni < Cp2 Ni <Cp2 Co <
Cp2V < Cp2Cr < Cp2Ti

 X-ray diffraction studies show that the ligands are in a staggered form in
the sandwich structure. While electron diffraction studies show them to
be in eclipsed configuration.

 Structure of ferrocene is pentagonal antiprismatic. In which, Fe ++ is


sandwiched between two five membered  - CP rings resulting in
pentagonal prism.

 Example of a triple decker is Cp3 Ni2. In which nickel atoms and


cyclopentadienyl rings have layered structure.

 In half sandwich compounds, there are other ligands present in the


molecule, in addition to cyclopentadienyl molecule, eg. cyclopentadinyl
– carbonyl vanadium complex, (5-C5H5) V (CO)4.

172
 Metallocenes should generally give aromatic reactions. But these
molecules do not remain stable in these reactions.

 The ligands in arene – organometallic 6- complexes are generally


benzene and benzene cycloheptatriene. The first 6- arene complex was
Cr (6 – C6H6)2, which was prepared by Fischer in 1955. Now all
transition metals with d2 – d8 configuration give 6- arene complexes.

 Although in 6-complexes aromatic properties are weak however they


give substitution, sulphonation, nitration etc reactions.

 In a molecular orbital description, planar C6H6 molecule combines its six


orbitals, in an analogous fashion to C5H5- groups, to give six molecular
orbitals. Out of these three are bonding and remaining three are
antibonding molecular orbitals. Antibonding molecular orbitals.
Analogous to ferrocene, these six molecular orbitals of one benzene
combine automatically with the set of other benzene and overlap with
metal orbitals of corresponding symmetry, resulting in the formation of
sets of bonding and antibonding molecular orbitals.

4.10 CHECK YOUR PROGRESS : THE KEY

1(a) (i) Butadiene-iron tricarbonyl, Fe(4-C4H6) (CO)3


(ii) x. Reaction of metal carbonyl with butadiene.
y. Synthesis by metal vapour

(iii) 4px

Molecular orbitals

Same symmetry

173
b. (i) Ru, Co and Mo
Metal
Four electrons (2 pairs of electrons)
(ii) Eight
Cyclo Octatetraene
Four
Cyclo-Octatetraene
2.(a) (i) Twocyclopentadinyl rings
Fe (5-C5H5)2
(ii) Pentagonalantiprismatic
X-ray diffraction
Cyclopentadinyl groups
(iii) Antibonding
Bonding
Non bonding
Nine
18 electron rule
(iv) Cp3 Ni2

(b) (i) Cr (6-C6H6)2

Fischer

1955
(ii) px
C5H 5

Six molecular orbitals

174
three
three
antibonding molecular orbitals
(iii) Octahedral
d2 sp3

________________________

175
UNIT-5 TRANSITION METAL COMPOUNDS WITH BONDS TO
HYDROGEN

STRUCTURE

5.1 Introduction

5.2 Objectives

5.3 Metal Hydrides

5.3.1 Hydrides of Transition Metals

5.3.2 Bonding in the Metallic Hydrides

5.3.3 Properties of Metallic Hydrides

5.3.4 Anions containing only a Transition Metal and Hydrogen.

5.4 Transition Metal Complexes with Bonds to Hydrogen

5.4.1 Carbonyl Hydrides

5.4.2 Tert. Phosphines and Arsines Hydrides.

5.4.3  - Cyclopentadienyl Hydrides

5.5.4 Cyanide Hydrides

5.5 Let Us Sum Up

5.6 Check Your Progress : The key

176
5.1 INTRODUCTION

Many of the transition metals, as well as the lanthanides and such


actinides as it has been possible to study, absorb hydrogen when heated in the
gas. This phenomenon is distinct from adsorption or chemisorption, which is
primarily a surface phenomenon, and involves penetration into the metal lattice.
The amount of gas taken up at equilibrium is a function of pressure and
temperature, and can be represented by a series of dissociation pressure
isotherms, The maximum hydrogen content is typically in the range MH0.1-0.2.
Formation of the solid solution is endothermic, whereas hydride
formation is an exothermic process. Hydriding is commonly carried out in the
temperature range 150º-400º, though some metals, including palladium, react at
lower temperatures and the equilibrium studies have often been extended to
700º or higher.
Except for actinium, nickel, palladium and cerium, they have lattices of a
different type from those of the parent metal; the hexagonal close-packed lattice
of some lanthanides, for example, is transformed to a face-centred cubic lattice
in the dihydrides.
Apart from these hydrides, number of transition metals give anions
containing the metal and hydrogen. Similarly number of transition metal
complexes form hydrogen derivatives containing metal hydrogen bond.
In this unit we shall discuss nature of transition metal hydride and
different transition metal complexes containing metal-hydrogen bond, In the
end of the unit, applications of these complexes in organic synthesis will also be
discussed.

177
5.2 OBJECTIVES

The main objective of this unit is to discuss nature of different


compounds of transition metals containing with bonds to hydrogen. After going
through this unit you should be able to :
 describe various transition metal hydrides, their methods of preparation,
nature of bonding and structure and principle characteristics,
 discuss nature and bonding of transition metal complexes with bonds to
hydrogen e.g. carbonyl hydrides, tert. phosphine and arsine hydrides,
  Cyclopentadienyl hydrides and cyanide hydrides, and

 describe the use of these compounds in organic synthesis.

5.3 METALLIC HYDRIDES

We know transition metals crystallise in closed packed structures.


Generally they have cubic closed packed or hexagonal closed pack structure.
Which have sufficient open space between the packed atoms, called voids or
interstices, in which small atoms of hydrogen are accommodated. Thus they
form interstitial hydrides. In these interstitial hydrides, hydrogen atoms are
generally linked by covalent bonds due to high e/r ratio of transition metal
atoms. Interstitial compounds are non stoichiometric compounds i.e. they
cannot be described by a fixed molecular formula. Their structure is generally
described by crystallographic rules, i.e. on the ratio of radii of transition metal
atom and hydrogen atom. In closed packed structure there are two types of
voids present, one tetrahedral (Th- voids) and the other octahedral void (Oh
voids). For tetrahedral voids the allowed radii ratio is 0.21-0.41, while that for
octahedral voids is 0.41-0.73. Due to rigid bonds these interstitial compounds
are quite hard.

178
5.3.1 Hydrides of Transition Metals
Titanium, zirconium and hafnium all react with hydrogen at a convenient
rate in the temperature range 300-400º.At such temperatures the hydride phase
has a considerable equilibrium dissociation pressure and the amount of
hydrogen taken up increases with the hydrogen pressure applied to the system;
compositions with hydrogen in excess of TiH1.9 may be obtained, but they are
more often in the range TiH 1.5-1.8. Similar considerations apply to all hydrides
made directly from the elements.

Titanium crystallizes with an hexagonal close-packed structure and, in a


different modification, with the bodycentred cubic structure. The dihydride has
a face-centred cubic fluorite structure. This is equivalent to a cubic close-
packed metal sub-lattice with hydrogen atoms in the tetrahedral holes, of which
there are two per metal atom, together with one octahedral hole per metal atom,
which is vacant. Below 310ºK this structure changes in the case of TiH2 to a
distorted tetragonal structure.

ZrH2 and HfH2 have higher transition temperatures for the


interconversion of the two corresponding forms. The structures of the
dihydrates of vanadium and niobium are similarly based on a face-centred cubic
metal sub-lattice.

The monohydrides VH and TaH both have body-centred tetragonal metal


sub-lattices, all three of the Group V metals having body-centred cubic lattices.
In addition NbH and TaH each have a body-centred orthorhobic modification.

Amongst VI group metals chromium forms hydride. This is formed


during the electrodeposition of metallic chromium from a sulphuric acid
solution of CrO3 under special conditions. One of the two phases has

179
compositions in the range CrH0.5-1 and has a hexagonal structure while the
other, which is much less stable, has a cubic structure with the upper limit of the
hydrogen content corresponding with the formula CrH1.7. This phase appears to
be similar in structure to the dihydrides referred to above.

A nickel hydride, NiH 0.6-0.7, has been made by a similar electrolytic


method. It decomposes slowly at room temperature to metal and hydrogen, but
neutron diffraction studies have shown the hydrogen atoms to occupy the
octahedral holes of the face-centred cubic lattice of the metal.

Palladium metal has long been known to absorb hydrogen readily, even
at room temperature Limiting compositions in the range PdH0.6-0.8 are observed.
The metal lattice of the hydride phase is face-centred cubic, as in the metal
itself, but the lattice parameter is increased by roughly 3 per cent. Neutron
diffraction studies have shown that the hydrogen atoms occupy the octahedral
holes in the metal structure and are randomly distributed. Copper hydride,
which differs greatly in its mode of preparation, properties and structure from
these metallic hydrides. Copper is the only transition metal, to form a well-
characterized hydride. Hydrogen has a low solubility in metallic copper and no
hydride, been known since 1844, when Wurtz prepared it by the reaction shown
below:

2Cu2+ + 3H2PO2- + 3H2O  2CuH + 3H2PO3- + 4H+

It is a red-brown crystalline material and is also produced by reducing


Cul with LiA1H4 in ether/pyridine, or by reducing aqueous CuSO4 with NaBH4.

The compound has a hexagonal wurtzite structure; this has been


established both by X-ray and by neutron diffraction. Thermal decomposition

180
occurs above about 50º. Decomposition by aqueous hydrochloric acid gives
CuCl and H2, and hydrogen is also evolved rapidly in alkaline solution. The
hydride is a reducing agent in aqueous media, converting, for example, chlorate
to chloride.

5.3.2 Bonding in Metallic Hydrides

Formation of the metallic hydrides is exothermic, in spite of the fact that


dissociation of molecular hydrogen to atoms requires 432 (103 keal) mole-1. To
compensate for this, the bonds formed must be strong.

Formerly these hydrides were classed with carbides, nitrides and borides
as interstitial compounds, and it was thought that hydrogen atoms, like other
small atoms, could be accommodated in interstices in the metal lattice
producing distortion but no change in type. In fact, the metal atoms in most of
these hydrides occupy a sub-lattice which is different from that of the parent
metal, and the interstitial compound concept also fails to describe the bonding
and changes in the physical properties of the metal which occur if it is hydrided.

Currently there are two quite distinct theories of bonding in metallic


hydrides. The first considers hydrogen to lose electrons to the conduction band
of the metal. Complete transfer of an electron to leave H+ is very improbable on
energetic grounds; it is more likely that there is a transfer of electron density,
leaving hydrogen with a fractional positive charge. This theory is supported by
studies of the migration of hydrogen under an applied potential in such
materials as hydrided palladium and titanium; hydrogen migrates to the
cathode.

The alternative theory, which postulates that H- is formed by loss of

181
electrons from the metal to hydrogen, also leads to the conclusion that there will
be a falling away in metallic properties as the hydrogen to metal ratio increases.

5.3.3 Properties of Metallic Hydrides

A great impetus to the study of the metallic hydrides discussed in this


section has come from the potential use of some in nuclear reactor technology.
A material such as zirconium hydride or deuteride, for example, where the
metal and hydrogen both have low thermal neutron capture cross-sections, is of
interest as a moderator material. Titanium and some of the other metals which
form hydrides have high neutron capture cross-sections and could find
specialized applications as shielding materials, Probably the most important of
the purely chemical properties is the susceptibility to atmospheric oxidation.
This varies widely : finely divided UH3, which is always formed when massive
uranium is hydrided, ignites spontaneously in air, whereas hydrides of metals in
the titanium group oxidize rapidly at temperatures in roughly the range 400-
600º, depending on the state of division. Most of the hydrides are stable to
water up to at least 100º. Most, including those of the lanthanide elements, are
quantitatively decomposed by acids and show reducing properties. Their
reactivity to common reagents is as a rule greater than that of the parent metals.

5.3.4 : Anions containing only a Transition Metal and Hydrogen :


Rhenium and technetium both form complexes containing the [MH 9]2-
ion. Treatment of potassium perrhenate with potassium in ethylenediamine
solution leads to precipitation of a solid which, after purification, is white and
analyses as K2ReH9. The isomorphous technetium compound is prepared
similarly, and various salts of these two anions are known. They may be heated
to over 200º with out decomposition and show strong reducing properties in

182
aqueous solution, in which slow hydrolytic decomposition occurs. Hydrogen is
evolved quantitatively on treating the salts with an aqueous acid, and the metal
is deposited.
The structure of K2ReH9 has been established by X-ray analysis and
neutron diffraction. The latter is particularly important as it enables the
positions of the hydrogen atoms to be determined. The crystal is hexagonal with
three molecules per unit cell. In the anion (Fig 5.1) six of the hydrogen atoms
are at the corners of a trigonal prism with the metal atom inside it, and there is
one hydrogen atom outside the centre of each of the prism faces in an equatorial
position.
The Re-H bonds are all approximately of the same length (1.68 A). The
proton n.m.r. spectrum shows a single high.field peak at 18.4 p.p.m. for the
rhenium compound and at 19.1 p.p.m. for the technetium compound, the latter
99
being broadened because of unresolved coupling with the Tc nucleus. All of
the hydrogen atoms thus appear to be equivalent on an n.m.r. time-scale, and all
undergo slow deuterium exchange in alkaline D2O. The infrared spectrum
shows the bending and stretching modes which are characteristics of the M-H
bonds.

Figure : 5.1 H environment of Re atom in ReH92-

183
Each hydrogen bonded to the metal atom may be regarded as a ligand
with a charge of -1 (i.e. as contributing two electrons to the metal atom). If the
latter is taken as being in the +7 state with sixty-eight electrons, addition of
eighteen electrons from the nine ligands gives an effective atomic number of
86, equal to that of radon. The nine electron pairs fully occupy all of the
available orbitals of the metal atom (5d56s6p3) and all of the nine hydrogen
orbitals.
The two compounds appear at the moment to be unique among transition
metal derivatives, though rhodium forms two compounds, Li 4RhH4 and
Li4RhH5, which may be similar. The former is made by heating rhodium
powder with LiAIH4 at 600º and reacts on further heating with hydrogen to give
the latter.

184
CHECK YOUR PROGRESS – 1
Notes : (1) Write Your answers in the space given bellows
(2) Compare your answers with those given at the end of this
unit.
(a) (i) The dihydride of titanium has FCC ...................... structure
with hydrogen atoms in ........................... holes, of which
there are two per metal atom. This structure changes to
........................... structure below 310K.
(ii) Wurtz prepared copper hydride with emperical formula
............... This hydride is a ........... agent in aqueous solution.
(iii) There are two current theories of bonding in metallic
hydrides :
(a) .....................................(b) .............................................
(b) (i) Re and Tc both form hydride complexes containing
................ ion.
(ii) In this anion ................... of the hydrogen atoms are at the
corner of ...................... prism, with metal atom inside.
(iii) Each hydrogen atom bonded to ...................... atom may be
regarded as a ligand with a ...........................

5.4 TRANSITION METAL COMPLEXES WITH BONDS TO


HYDROGEN

The carbonyl hydrides of iron and cobalt, which were discovered by


Hieber and his co-workers in 1931, provide the earliest examples of compounds
with a   bond between hydrogen and a transition metal. The nature of the
bond was not established for some time, but many carbonyl hydrides have since

185
been isolated and they now constitute an important facet of carbonyl chemistry.
Other ligands, notably tertiary arsines and phosphines, the cyclopentadienyl
radical and the cyanide ion, have, however, also been found to stabilize the M-
H bond in transition metal complexes. The chief interest in these compounds
centres on the metal-hydrogen bond, and they are therefore considered here as
hydrides. Only in compounds, K2 ReH9 and its technetium analogue, is
hydrogen with certainty to be   bonded to a transition metal in the absence of
other ligands.

The characteristic common to ligands such as tertiary phosphines and the


cyanide ion is that they produce strong ligand fields. They also exert a similar
influence in stabilizing the metal-carbon   bond in transition metal alkyls and
aryls. Chatt and Shaw have suggested that one important factor in determining
M-C bond stability is the energy gap  between the highest occupied electron
level and the lowest unoccupied level; the greater  the higher is the stability.
Since the ligands in question all increase,  , this effect may be related to their
influence on both the M-C and the M-H bond are established by the standard
methods, though location of the hydrogen atom by X-ray diffraction is difficult
and neutron diffraction is preferred. The main diagnostic method is the use of
the 1H n.m.r. spectrum, where high-field shifts in the rang r = 12-45 are
observed, as for the carbonyl hydrides. In the infrared spectrum metal-hydrogen
stretching frequencies occur in the range 1700-2200 Cm-1, which are reduced by
the factor of 2 on deuteration. In most of the complexes to be discussed

hydrogen behaves as a strong-field ligand.

5..4.1 Carbonyl Hydrides


Some metal carbonyls dissolve in alkali (with the loss of a molecule of
carbon monoxide in the case of mononuclear carbonyls) and form carbonylate

186
anions. Iron pentacarbonyl, for example, gives a solution which is colourless i
the absence of air and which on treatment with dilute mineral acid evolves iron
carbonyl hydride (H2Fe(CO)4) as an evil-smelling gas which can be condensed
to a white solid melting at -70º. It decomposes rapidly above-10º, giving
hydrogen and products of decomposition of the Fe(CO)4 radical. A number of
other carbonyl hydrides, among them HMn(CO)5, HRe(CO)5, H2Ru(CO)4,
H2Os(CO)4 and HCo(CO)4, can be obtained by acidification of solutions
containing carbonylate anions obtained, Other methods of preparation include:
NaBH4
Fe(CO 4 )I 2 
 H 2 Fe(CO) 4
THF

200º
Mn 2 (CO ) 10  H 2 
 2HMn (CO ) 5
200atm

150º
1
Co  4CO  H 2   HCo(CO) 4
2
50atm

The most stable of these compounds with respect to thermal


decomposition are HMn(CO)5 and H2Os(CO)4, both colourless liquids which
are stable up to about 80º and 100º respectively. Most reactions of HMn (CO)5
involve replacement of the hydrogen atom (e.g. it reacts with Me2Cd and with
GeH4 to give Cd[Mn(CO)5]2 and H2Ge[Mn(CO)5]2 respectively), but Ph3P
displaces a molecule of CO to form HMn (CO)4(PPh3). Substitution of
triphenylphosphine in other carbonyl hydrides enhances the stability : HCo
(CO)3 (PPh3) and HV(CO)5(PPh3), for example, are well-defined species,
whereas HCo (CO)4 decomposes above – 20º and HV(CO)6 has not yet been
prepared.

187
The acidities of mononuclear carbonyl hydrides vary very widely:
HCo(CO)4, though only slightly soluble in water, is as strong as a mineral acid
in methanol; for H2Fe(CO)4 pK1 and pK2 are 4.5 and 1.4 respectively; and for
HMn (CO)5 pK is 7. It seems clear that the hydrogen atoms in all these
compounds are bonded to the metal, though only for HMn(CO)5 is the structure
known in detail: the molecule is octahedral, with the Mn-H distance equal to
1.60A. Two physical properties may be used to show that metal-hydrogen
stertching vibration, which occurs at 2200-1700 Cm-1, is lowered by the
theoretical factor of 2 on deuteration, and transition metal hydrides have

characteristic high-field 1H n.m.r. spectra in the range r 12-45 (17.5 for


HMn(CO)5 and 20 for HCo (CO)4). The structure of the substituted carbonyl
hydride (Ph3P)3 Rh(CO)H has also been determined by X-ray crystallography;
this molecule is a trigonal bipyramid with hydrogen and carbon monoxide
occupying the apical positions.

Many di-or polynuclear carbonyl hydrides have been reported, but their
formulae are not always related to those of known carbonylate anions, and
many of the structures assigned to them rest only on spectroscopic evidence.
We may, however, mention HRe2Mn(CO)14 (Fig 5.2) and the anion [HCr2
(CO)10]- (Fig. 5.3) In each case spectroscopic and diffraction data are consistent
with a linear symmetrical hydrogen bridge and eclipsed carbonyl groups on the
metal atoms bonded to hydrogen. The structure of [HFe3(CO)11]- is closely
related to that of Fe3 (CO)12 and can be regarded as the latter with one bridging
carbonyl replaced by hydrogen. In [HFe2(CO8]- a hydride ion similarly replaces
a bridging carbonyl group in the Fe2(CO)9 structure. Among several carbonyl
hydrides obtained by dissolution of metal carbonyls in alkali to give
unidentified coloured products, and subsequent acidification, are H3Mn3 (CO)12

188
(from Mn2 (CO)10), and H4Os4(CO)12 and H2Os4(CO)13 (from Os3(CO)12).
Evidently considerable molecular rearrangements can take place in what might
seem to be a simple process.

Figure 5.2 Figure 5.3


Addition of hydrogen in Rh(II), Ir(II) and Pt (O) complexes is a common
reaction. Generally many complex hydrides of transition metals have been
prepared by this method.

H2 molecule can link (coordinate) with metal atom with out breaking
H-H bond. The first such complex was [W(CO)2 (H2) (P' Pr3)2 (Fig 5.4). Now a
large number of such complexes have been prepared, which may be regarded as
the link between H2 molecule and dihydrido complexes. Molecular Orbital
descriptions indicate that electron density from H-H bond is transferred to
vacant orbital of metal, along with formation of back   bonding in  * orbtal
of H2.

Figure 5.4

189
Similarly Brown and associates have confirmed linking of CH ----Fe in
[Fe(3.C8H13) {P(OMe)3}3]- complex using neutron diffraction method. While
Calvart and Shaple have on the basis of NMR studies of triosmium complex,
given proof of C.H-Os bond (Fig 5.5)

Figure 5.5

This type of coordination of C-H bond has been called 'Agostic


interaction. Which is supposed to be three centered two electron bond
analogous to the bonds present in B-H-B or W-H-W.

5.4.2 Tert. Phosphines and Arsines Hydrides.


Transition metal hydrides with these two types of ligand are the most
numerous, and also among the most stable, of the compounds under discussion.
The first such compound to be prepared was trans-[PtHCl (PEt3)2], which was
obtained by reducing cis[PtCl2(PEt3)2] at 90º with a dilute solution of hydrazine
hydrate. Reduction of a complex halide is a fairly general method and various
other reducing agents may be employed, such as LiAIH4 in tetrahydrofuran,
NaBH4 in water, or hydrogen, as in the reaction.

cis  [PtCl2 (PEt 3 ) 2 ]    trans  [PtHCl(PEt 3 ) 2 ]


H 95º at 50atm
2,

ethanol

Reduction may be brought about in some cases by an alcohol in the presence of


a base ; for example,

190
IrCl3 (PEt2Ph)2 + OH- + C2H5 OH
-
 IrHCl2(PEt2Ph)2 + CH3CHO + H2O + Cl
In this particular case all three chlorine atoms may be replaced by
hydrogen if excess of reagent is used. By using the deuterated alcohol
CH3CD2OH in the above reaction, it is found that the hydrogen introduced into
the metal complex is that bonded originally to the   carbon in the alcohol.
Reaction is believed to involve replacement of chlorine by the ethoxide ion with
subsequent transfer of hydrogen from the ethyl group to the metal. The
intermediate step can thus be formulated as

Thermal decomposition of alkyl derivatives of some transition metals can


also yield the hydride, trans [PtCl(C2H5)(PEt3)2], for example, giving trans
[PtHCl(PEt3)2], similarly, a volatile iron hydride complex is formed in the
following reaction, in which iron is dissolved in the diphosphine in a hydrogen
atmosphere:
Fe+H2 + 2O-C6H4(PEt2)2  FeH2[0-C6H4(PEt2)2]2

Various phosphines and arsines have been employed, and a large number
of such derivatives of metals in Groups VII and VIII isolated.

Hydrogen functions as a normal ligand in these complexes and often


exercises a strong trans effect. A number of isomers have been identified on the
basis of measurements of dipole moment and proton n.m.r. spectra, in which
31
coupling with P and with other protons in the molecule yields valuable
structural information. Hydrogen may sometimes be replaced by other ligands
as, for example, in the reaction shown below :

191
IrH2 Cl(PEt3)3 dryHCl
 IrHCl2 (PEt3)3

If the complex is treated with a solution of chlorine in chloroform the


product is IrCl4 (PEt3)2. In other cases, addition reactions may occur, as in the
conversion of PtHCl(PEt3)2 to PtH2Cl2(PEt3)2 by hydrogen chloride.

In addition to the triphenylphosphine-substituted carbonyl hydrides


already mentioned, many others are known. Indeed, the combination of hydride,
carbonyl and triphenylphosphine as ligands for the platinum metals is so
favourable that several compounds of this type can be synthesized easily, a
typical example being.

Os(CO)5 130  (Ph P)Os(CO) H 2 / THF H Os(CO) (PPh )


130º

º at120atm 3 3
130
Vat  2
120atm
2 3 2

5.4.3   Cyclopentadienyl Hydrides


Like the tertiary phosphines, the cyclopentadienyl radical may occur as a
ligand in association with carbon monoxide in the carbonyl hydrides. Both the
preparative methods for the cyclopentadienyl carbonyl hydrides and their
reactions are very similar to those of the carbonyl hydrides. They can, for
example, be prepared by reduction of a halide (e.g.   C3H3Fe(CO)2Cl), or by
acidification of the sodium salt of   cyclopentadienyl carbonylate anion ; for
example,

Mo(CO)6  Na  C5 H5  Na  [  C5 H5 Mo(CO)3 ]
   C5 H 5 Mo(CO) 3 H

The reactions that are of interest are those of the M-H bond, such as its
conversion to an M-Cl bond by mild chlorinating agents (e.g. CHCl3), and the
loss of hydrogen on heating, with formation of a binuclear complex, Addition
of olefins across the M-H bond also occurs (e.g.   C5H5 Fe(CO)2H with C2F4

192
gives   C5H5 Fe (CO)2 CF2 CF2H(, while diazomethane converts   C, H, Mo
(CO)3H to   C5H5 Mo(CO)3 (CH3).
A number of hydrides are also known in which the cyclopentadienyl
radical and hydrogen are the sole ligands bonded to the transition metal. The
first to be prepared was [ReH(   C5H5)2], made by the reaction

Re Cl 5  Na(C5 H 5 THF

 Re H(C5 H 5 ) 2  NaBH 4

The related compounds MoH2 (   C5H5)2, WH2 (   C5H5)2 and TaH3


(   C5H5)2 are all formed similarly.

The structure of MoH2(   C5H5)2 (apart from the position of the H


atoms) has been determined by X-ray analysis and shows the two rings to be
situated as shown below (Fig. 5.6) There is some evidence for a similar oblique
ring structure in the other compounds.

Figure 5.6 Figure 5.7

All are crystalline solids which sublime in high vacuum and are soluble
in organic solvents. They are unaffected by water or alkali but oxidize in the air.
Reaction with chloroform converts the M-H bond to M-Cl.

193
5.4.4 Cyanide Hydride
Hydrogen is absorbed by an aqueous solution of a cobalt salt to which
cyanide ion has been added to form [HCo(CN)5]3- and the proton n.m.r.
spectrum of the product shows a chemical shift of 17.5 p.p.m. relative to water.
This high value makes it certain that a Co-H bond is present in the complex.
Slow decomposition of the solution occurs in the absence of oxygen at room
temperature and it is very sensitive to atmospheric oxidation. The oxidation
product is the anion [Co(CN)5OOH]3-, the potassium salt of which has been
prepared by hydrolysis of K6 [(CN)5Co-O- OCo (CN)5], and which has a
characteristic electronic absorption spectrum. Solutions containing the cobalt
cyanide hydride can act as homogeneous catalysts in various hydrogenation
reactions (e.g. the conversion of styrene to ethylbenzene). Reaction also occurs
with tetrafluoroethylene to give the ion [Co(CN)5CF2CF2H]3-, which is again
strong support for the presence of the Co-H bond in the ion. A solid salt NaCs2
[Co(CN)5H] has recently been isolated.

194
CHECK YOUR PROGRESS – 2

Notes : (1) Write Your answers in the space given bellows


(2) Compare your answers with those given at the end of this
unit.

(a) (i) The iron carbonyl hydride, ....................., is an .....................


(ii) In H Re2 Mn (CO)14 and [H Cr2 (CO)10]- both spectroscopic
and ................... data indicate a linear symmetrical ..............
bridge and ................. carbonyl group on the metal atoms
bonded to ...................
(iii) For complexes such as [W(CO)2 (H2) (PPBr3)2, MOT
description indicate electron density from ..............................
is transfered to ..................... orbital of metal, along with
formation of back ......................... in  * orbital of .................

(b) (i) Coordination of C-H bond has been called


............................... ...................................
(ii) In tert. phasphine hydrides .................... functions as a
normal ligand, and often exercises strong ................. effect.
(iii) The combinatoin of hydride, carbonyl and Triphenyl
phosphine as ligands for the platinum metals are quite
favourable. The osmium complex has formula ..................
(iv) Solution containing corbonyl cyanide hydride Cobalt reacts
with tetrafluoro ethylene to give. ........................... which is a
strong support for the presence of the ...................... bond in
the ion.

195
5.5 LET US SUM UP

After going through this unit, you would have achieved the objectives
stated earlier. Let us recall what we have discussed :

 Many of the transition metals, as well as the lanthanides and such


actinides as it has been possible to study, absorb hydrogen when heated
in the gas.

 Hydriding is commonly carried out in the temperature range 150º-400º,


though some metals, including palladium, react at lower temperatures
and the equilibrium studies have been extended to 700º or higher.

 Ti, Zr and Hf all react with hydrogen at a convenient rate in the


temperature range 300-400º.

 The dihydrides of Ti, Zr and Hf have MH2 formula. Titanium crystallises


with an hexagonal close packed structure. The dihydride has a FCC
fluorite with hydrogen in the tetrahedral holes.

 The dihydrides of Vanadium and niobium are similarly based on a face


centred cubic in metal sub lattice.

 The monohydrides VH and TaH both have body centred tetragonal metal
sublattice, in addition these have a body centred orthorhombic
modification.

 Amongst VI group metals only chromium forms hydride with formula


CrH1.7. It has structure simitar to the dihydrides discussed above.

 Nickel and palladium hydrides (NiH .7), PdH 0.8) are formed by

196
absorbing hydrogen at low temperature.

 Copper is the only transition metal to form a well characterised hydride.


Wurtz prepared CuH in 1844. The compound has a hexagonal wurtzite
structure, established by both X-ray and neutron diffraction.

 Formerly, like carbides, nitrides and borides, hydrides were also


considered to have interstitial structure.

 Currently two theories of bonding in metallic hydrides are common:

The first considers hydrogen to lose electrons to the conduction bond of


the metal.

The alternative theory postulates that H- is formed by loss of electrons


from metal to hydrogen, This leads to the conclusion that there will be falling
away in metallic properties as the hydrogen to metal ratio increases.

 A great impetus to the study of metallic hydrides has come from the
potential use of some in nuclear reactor technology. Zirconium hydride,
with the metal and hydrogen both having low thermal neutron capture
cross section is important in this respect..

 Titanium and some of the other metals which form hydrides have high
neutron capture cross section and could find specialized applications as
shielding material.

 Rhenium and technetium both form complexes containing the [MH 9]2- X-
ray and neutron diffraction studies show that the crystal of K 2ReH9 has
hexagonal structure with three molecules per unit cell. In the anion six of

197
the hydrogen atoms are at the corners of a trigonal prism with the metal
atom in side it, and there is one hydrogen atom outside the centre of each
of the prism faces in an equatorial position.

 A number of carbonyl hydrides, H2Fe (CO)4, H Mn (CO)5, H Re (CO)5,


H2 Ru(CO)4, H2Os (CO)4 and HCo (CO)4 have been obtained by
acidification of solution containing carbonylate anions. The most stable
of these with respect to thermal decomposition are HMn (CO)5 and H2 Os
(CO)4 both colourless liquids.

 Substitution of triphenyl phosphine in carbonyl hydrides enhances the


stability e.g. HCo (CO)3 (PPh3) and HV(CO)3 (PPh3) are quite stable well
defined species.

 Many di or polynuclear carbonyl hydrides have been reported. HRe2


Mn(CO)14 and the anion [H Cr2 (CO)10]-, in their spectroscopic and
diffraction studies show a linear symmetrical hydrogen bridge and
eclipsed carbonyl groups on the metal bonded to hydrogen.

 Many complex hydrides of transition metals have been prepared by


addition of hydrogen to metal complexes e.g. complexes of Rh(II), Ir(II)
and Pt (0).

 H2 molecule can link (coordinate) with metal atom without breaking H-H
bond. The first such complex was [W(CO)2 (H2) (PPBr3)2

Molecular orbital description indicate that electron density from H-H


bond is transferred to vacant orbital of metal, along with formation of
back   bonding in  * orbital of H2.

198
 Brown and associates indicated that there is CH-Fe link in [Fe (n3-
C8H13) {P(OMe)3}3}- complex, using neutron diffraction studies.

 Calvart and Shaple have, on the basis of NMR studies of tri osmium
complex, given proof of C-H-Os bond. This type of coordination of C-H
bond has been called 'Agostic interaction' which is supposed to be three
centred two electron bond analogous to the bonds present in B-H-B and
WHW.

 Transition metal hydrides with tert phosphine was trans [Pt HCl (PEt 3)2],
by reducing Cis [PtCl2 (PEt3)2] at 90º with dilute solution of hydrazine
hydrate.

 Various phosphine and arsines have been employed and a large number
of such derivatives of metals in groups VII and VIII isolated.

Hydrogen functions as a normal ligand in these complexes and often


exercises strong trans-effect.

A number of isomers have been identified on the basis of measurements


31
of dipole moment and proton n.m.r. spectra in which coupling with P
and with other protons in the molecule yield valuable structural
information.

 Like the tert phosphines, the cyclopentadienyl radical may occur as a


ligand in association with carbon monoxide in the carbonyl hydrides.

 A number of hydrides are also known in which the cyclopentadienyl


radical and hydrogen are the sole ligands bonded to transition metal.

199
 The important compounds prepared in this series are ReH (5 C5H5)2,
MoH2 (   C5H5)3 WH2 ( C5H5)2 and TaH2 (   C5H5)2.

The structure of MoH2 (   C5H5)2 has been determined by X-ray


analysis show oblique ring structure in these compounds.

 Hydrogen is absorbed by an aqueous solution of a cobalt salt to which


cyanide ion has been added to form [HCo (CN)5]3- The n.m.r. spectrum
of the product shows that a Co-H bond is present in the complex.

 Solutions of Cobalt cyanide hydride can act as homogeneous catalysts in


various hydrogenation reactions.

5.6 CHECK YOUR PROGRESS : THE KEY

1 (A) (i) Fluorite


Tetrahedral
distorted tetragonal
(ii) CuH
reducing agent
(iii) (a) The first one considers hydrogen loses electron to
conduction band of metal.
(b) An alternate theory postulates that H- is formed by
loss of electron from the metal to hydrogen.
1(b) (i) MH92-
(ii) Six
Hexagonal
(iii) Metal
-1 charged

200
2(b) (a) (i) H2 Fe (CO)4
evil smelling gas
(ii) diffraction
hydrogen
eclipsed
hydrogen
(iii) H-H bond
Vacant
  bonding

H2

(b) (i) Agostic interaction


(ii) hydrogen
trans
(iii) H2Os (CO)2 (PPh3)2
(iv) [Co(CN)5 CF2.CF2 H]3-
Co- H

201
UNIT-6 HOMOGENEOUS CATALYSIS-I

Structure:
6.1 Introduction

6.2 Objectives

6.3 Homogeneous Catalysis

6.4 Stoichiometric Reactions for Catalysis

6.4.1 Reactions of Coordinated Alkylidenes

6.4.2 Reactions of Coordinated Alkylidynes

6.4.3 Reactions of Coordinated Carbenes

6.4.4 Reactions of Coordinated Alkene

6.4.5 Reactions of Coordinated Alkynes

6.4.6 Reactions of Coordinated Allyl groups

6.4.7 Reactions of Coordinated Dienes

6.4.8 Reactions of Coordinated Cyclopentadienyl

6.4.9 Reactions of Coordinated Arenes

6.5 Let Us Sum Up.

6.6 Check Your Progress: The Key

202
6.1 INTRODUCTION

We are aware that a catalyst is a substance which increases the rate of a


chemical reaction without being used up in the reaction. According to modern
view, a catalyst form an intermediate compound and is finally regenerated. By
its involvement in reaction mechanism, catalyst lowers the free energy of
activation and thus increases the rate of a reaction

Conversion of SO2 in SO3 in absence of a catalyst is very slow


2 SO2 + O2 2SO3 (uncatalyzed-slow)
But when nitric oxide (NO) is added, a more efficient path is introduced.
2 NO + O2  2NO2
2 (NO2 + SO2 NO + SO3)
and this results into an increase in the rate of the reaction.

A catalyst is effective only when it comes in contact with reactant(s).


When the catalyst mixes homogeneously with the reactant (s) and forms a
single phase, the catalyst is said to be homogeneous and this kind of catalysis is
HOMOGENEOUS catalysis and when it forms a separate phase (usually a
solid phase) it is said to be heterogeneous and catalysis is HETEROGENEOUS
CATALYSIS. Catalytic oxidation of SO2 to SO3 in the presence of NO
(reaction cited above) is an example of homogeneous catalysis. An example of
heterogeneous catalysis is manufacture of sulphuric acid in contact process by
using V2O5as a catalyst.

Transition metal complexes (which may or may not be isolable) having at


least one metal-carbon bond have shown considerable potential as intermediates
in synthetic procedures. Many of these are truly catalytic in nature, as these can

203
be represented in a cycle form with the continuous regeneration of the original
active catalyst. Such catalytic reactions have achieved greater importance in
industrial processes, but the role of transition metal organometallics as synthetic
(stoichiometric) reagents is also beginning to make an impact in
organometallic/organic synthesis.

The effects of electronic changes or/and steric factors on the reactivity of


a substrate (ligand) on being attached through a carbon atom to a metal centre
have also been discussed. These modifications in the reactivity of the ligand
may generate changes of the types (e.g., electrophilic, nucleophilic, coupling,
and isomerization): (i) favourable (activation) to a higher reactivity of the
ligand due to attachment to a transition metal centre; (ii) inhibition of reactivity
(protection) towards reagents that normally interact with the parent substrate
(i.e. uncoordinated ligand); and (iii) stabilization of such species as could be
used for the synthesis of new and exciting organic compounds.

In this unit we shall discuss various stoichiometric reactions of


organometallic compounds of transition metals.

6.2 OBJECTIVES

The main aim of this unit is to study various stoichiometric reactions of


transition metal organometallic compounds useful in organic synthesis. After
going through this unit you should be able to:

 discuss importance of stoichiometric reactions in organic synthesis.

 describe the use of different stoichiometric reactions of coordinated


alkylidene, alkylidynes, carbenes, alkene, alkynes, allyls, diens,

204
cyclopentadienyl and arenes with reference to their important synthetic
uses and

 discuss and explain important organometallic compounds as


homogeneous catalysts.

6.3 HOMOGENEOUS CATALYSIS

As has been mentioned a catalyst is one which is effective only when it


comes in contact with reactants, when the catalyst mixes homogeneously with
the reactants and forms a single phase, the catalyst is said to homogeneous
catalyst.

Further, the simplest definition of a catalyst is a species which facilitates


a particular reaction without being consumed in the process; it may be
regenerated in its original form but sometimes, in a lower or higher oxidation
state also. There are various theories of catalysis, but the most common one
involves the formation of intermediate compounds (often transient or/and non-
isolable); the ability of transition metals to form labile complexes with
molecules such as hydrogen, alkenes, allyls, arenes, and carbon monoxide has
led to a flurry of activity in designing various synthetic (catalytic and
stoichiometric) processes in which the formation and scission of metal carbon
bonds play an important role. It is such synthetic and catalytic processes that we
are going to discuss in detail in this unit.

Another commonly accepted view of the role of a catalyst is that it


lowers the activation energy barrier for a thermodynamically allowed (but
kinetically slow) reaction resulting in an enhancement of the rate of the process.
Further, in cases where alternative reaction paths are feasible, a catalyst may

205
enhance product specificity by lowering the activation barrier for one path or by
raising it for another. Reactions at a catalytic centre or site are believed to
involve the intermediate formation of weak catalyst-reactant bonds which have
the effect of loosening the bonds in the reactants prior to reaction. Many
catalytic reactions taking place in homogeneous (both catalyst and reactants are
in one phase) solution have been interpreted in terms of the formation of an
activated (or intermediate) complex.

6.4 STOICHIOMETRIC REACTIONS FOR CATALYSIS

In addition to the novel roles of organo transition metal complexes as


catalysts, further advances are being continuously made in the applications of
these organometallics especially as stoichiometric reagents. The main
distinguishing feature between catalytic and stoichiometric reagents used as
initiators in synthetic procedures, is that the latter are generally not regenerated
as such but are converted into other species. Further, the synthetic stability of an
oraganometallic stoichiometric reagent depent on two key factors i.e. speed and
selectivity of the desired reaction.

Important stoichiometric synthesis reactions are as follows:

1. Reaction of coordinated alkylidenes.


2. Reaction of coordinated alkylidynes.

3. Reaction of coordinated carbenes


4. Reaction of coordinated alkenes

5. Reaction of coordinated alkynes

6. Reaction of coordinated allyl groups

7. Reaction of coordinated dienes

206
8. Reactions of coordinated cyclopentadienyls
9. Reaction of coordinated arenes.

6.4.1 REACTIONS OF COORDINATED ALKYLIDENES

Alkylidene complexes (M=CRR') are chemically very labile and the


carbon atom bound to the metal exhibits a strong nucleophilic character,
whereas metal centre is electrophilic. The chemical and spectroscopic studies
show that M=C bond, due to low electronegativity of metal atom (placed at left
side in d-block series), is polarised such that the carbon atom attached to metal
develops negative charge. Corresponding molecular orbital explainations show
that pz orbital of CR2 group is of lower energy compared to dx orbital of metal
atom. As a result, π electron density concentrates on carbon atom. Thus, this
shows strong nucleophilic propery, while the metal atom remains electrophilic.

The reactions of these compounds are divided in to three groups.

(d) Reactions of nucleophilic carbon.

(e) Reaction with unsaturated organic compounds, and


(f) Decomposition reactions.

(a) Reactions of nucleophilic carbon.

(i) The alkylidene complexes (mainly of Nb and Ta) are strongly


nucleophilic, and therefore, exhibit greater tendency towards protonation
reactions, e.g.:
low temp.
(Me3CCH2)3 Ta(:CHCMe3)+HCl TaCl(CH2CMe3)4

(v) With Lewis acids such as Al2Me6 also, these form addition complexes,
e.g.:

207

Cp 2Ti ( CH 2 ) Me  Me3 SiBr [Cp 2Ti(CH 2 Si Me3 ) Me] Br 

(C5H5)2TaMe(:CH2)+1/2 Al2Me6 Mel TaMe(CH2AlMe3) (C5H5)2

(iii) Interactions with organic halides have been shown to proceed via SN2
mechanism, e.g.:
Mel
TaMe(:CH2)(5-C5H5)2 TalMe((5-C5H4) ((5-C5H5)2

(iv) Addition with phosphine ligands - Unsaturated phosphine ligand


(Nucleophilic) adds to electrophilic metal centre:

TaMe( CH 2 ) (CHCMe3 )  2PMe3  (Me3CCH 2 ) Ta ( CHMe3 ) ( PMe3 ) 2

(vi) Reaction with carbonyl compounds (Result of combined effect of


nucleophilicity of alkylidene carbon and oxygen affinity of metal centre);
eg. reactions of (Me3CCH2) Ta (=CH CMe3) (PMe3)2 :

(i) Reaction with aldehyde

Me3C CH 2 3 Ta CH CMe3   PhCHO  PhCH  CHCMe3  Me3CCH 2 3 TaO

(ii) Reaction with Ketone

Me3C CH 2 3 Ta CH CMe3   Me2 CO  MeC  CHCMe3  Me3CCH 2 3 TaO

(iii) Reaction with Ester

Me3C CH 2 3 Ta CH CMe3   Me2CO2 Et  Me3CCH 2 3 TaO  EtO MeC  CHCMe3

(iv) Reaction with CO2 :


Me3C CH 2 3Ta CH CMe3   CO2  Me3CCH  C  CHCMe3  Me3CCH 2 2 Ta ( O)OH

208
(b) Reaction with Unsaturated Organic Compounds
In view of their proposed role in alkene metathesis reactions the
interactions of unsaturated compounds with alkylidene complexes assumes
special significance:

(c) Decomposition reactions. The alkylidene complexes are more labile even
at room temperature, that they undergo decomposition reactions.

209
Applications in Organic Synthesis

The reactions given in section 6.4.1 indicate clearly that alkylidene


complexes may be utilise in organic synthesis. The most important reactions in
this respect are:

(iii) Alkene – exchange and addition reactions of unsaturated organic


compounds, and

(iv) Reactions with different carbonyl compounds

(See, 2.4.3 (b) and 2.4.3 (a) (v) reactions)


Reactions of Organic Copper
The field of organocopper chemistry has growth dramatically during the
past two decades. In fact, these reagents have become so important that modern
textbooks on introductory organic chemistry expose students to organic copper
chemistry.

The reagent adds selectively at the β-carbon of an α, β-unsaturated


carbonyl system, and also has a unique ability to effect replacement of most
types of halogen atoms by methyl groups. Lithium dimethylcuprate reacts with
allylic acetates by an SN2 mechanism. It has been found to react with epoxides
to give open ring alkylated alcohols. It also adds to acetylene esters. In addition,
there are examples of similar reactions involving branched alkyl, phenyl and
vinyl copper reagents. Several specific examples are mentioned below; the
chemical reactivity displayed by the cuprate reagents is due to a powerful
nucleophilicity toward carbon, along with a strong preference for reaction at
alkene or halide site compared to carbonyl groups.

The Specific reactions of LiCu Me2 with reference to Organic synthesis

210
are:

1. Halogen Substitution

(i) Tross PhCH=CH Br + Li Cu Me2Tross PhCH = CH Me

(ii) C6 H5 I + Li Cu Me2  C6 H5 Me

(iii) C5 H11 Br + Li [Cu But2]  But (CH2)4 CH3

(iv)

(v)

2. Conjugated Additions

(i)

(ii)

(iii)

211
3. Alkylation of Allyl Acetate

4. Alkylation of Epoxides

(i)

(ii)

5. Formation Ketone from Acid Chloride

(i)

(ii)

6.4.2 Reactions of Coordinated Alkylidynes


There are two important reaction of alkylidyne complexes, which are used in organic
synthesis as catalyst :
1. Synthesis of new alkynes (Exchange Reaction) :

W (C CMe3 )(OC Me3 ) 3  RC  CR W ( CR)(O CMe3 ) 3  RC  C CMe3


Excess

2. Insertion Reaction CMe

W (C CMe3 )(dme) Cl 3  Me C  C Me  Cl 3 W Me

Me

212
6.4.3. Reactions of Coordinated Carbenes
As we know in carbene complexes, whre metal ion is nucleophilic,
carbene carbon is electrophilic. These complexes give various types of
reactions:

1. Displacement of ligands coordinated with metal :

OMe
(i) (CO) 5 Cr  C (OMe) R  PR3  (CO) 4 ( PR3 )Cr  C
R

Substituti on
(ii) (CO) 5 Cr  C (OMe) R  Py     (CO) 5 Cr Py  CH 2  CH (OMe)
and fission

2. Displacement on Carbene Carbon:


NR'R"
(i) (CO)5 Cr  C (OMe) R  HNR' R"  (CO)5 Cr  C
R

N = CPh2
(ii) (CO)5 Cr = C (OMe)R + HN = CPh2  (CO)5 Cr = C R

Nucleophilic Ph
(iii) (CO) 5 Cr  C (OMe)Ph  Li Ph (CO) 5 Cr  C
Addition Ph

3. Reaction on side chain of carbene:


OMe
(CO)5 Cr = C (OMe)R + HC  CPh (CO)5 Cr = C CH=C(Ph)R

4. Oxidation and Reduction of metal :

213
5. Insertion on double bond

(i)

OMe OMe
(ii) (CO) 5 Cr  C  Ca(CN )  (CO) 5 Cr  N  C  CH
Ph Ph

Applications in Oraganic Synthesis


Carbene complexes are used for synthesis of various organic compounds
by decomfolexation. e.g.

2. Alkene by dimerisation of carbene ligand:

i.

1300
ii. Heat

214
2. New alkene from decomplexed carbene :

CH2=CHOR
i.
500C

ii.

3. Cyclopropene and vinyl ether by the reaction of electro deficient alkene


or diazomethane:
(i)

(ii)

4. Ester from decomplexed carbene by reduction:

215
4. Synthesis of special compound containing alkyle, carbene and
carbyne ligands (Churchill and Youngs, 1979):

CHECK YOUR PROGRESS-1

Notes: 1. Write your answers in the space given below.

2. Compare your answers with those given at the end of the unit.

(a) (i) In association with the catalyst, reactions of reactants become


possible at ................................ This results in ................................
reaction rate. Their efficiency is expressed in terms of ....................
..............................

(ii) The important reactions of alkylidene may be divided into three


groups :

(x) ..........................................

216
(y) ..........................................

(z) ..........................................

(iii) Reactions of dimethyl cuprate with methyl phenoxide gives ...........


....................................

(iv) Alkene, with electron deficiency resulted due to decomplexation,


reacts with diazomethane to give -

(x) ..........................................

(y) ..........................................

(v) Coordinated alkene after decarboxylation by reduction give ...........


.............................

(vi) .................................. released as a result of decarboxylation, after


reaction with alkene reagent gives ...................................

6.4.4 Reactions of Coordinated Alkenes

Chemical properties of alkene complexes depend on the following facts:


(d) For metal atoms alkenes are weak ligands hence can be replaced
by strong ligands like cyanide, t-phosphine etc.
(e) After coordination with metal, electron-density in -bonding
orbital decreases, but increases in antibonding * orbital, As a
result alkene molecule is activated and takes part in different types
of reaction. These reactions are important for industries.
(f) 2- alkene complexes give many products using nucleophilic

217
reactions.

Stoichiometric reactions of transition metal alkene complexes: (i)


Nuclecophilic attack on 2-alkene complexes. The nucleophilic attack can occur
in three different ways: (a) the nucleophile displaces the alkene, (b) the
nucleophile attacks the metal but displaces ligands other than the alkene, and (c)
the nucleophile attacks at an alkenic carbon of the alkene. These general types
of reactions are summarized in schemes I to V:

218
219
Scheme-V

Reactions lnvolving Metal – Alkene Intermediates in Homogeneous


Catalyzed Reactions. The consequence of alkene – metal interaction include a
lowering of the electron density of the  bonding orbital and an increase in the
electron density of the  orbital. The overall effect of alkene coordination a
metal centre brings about excitation of alkene -bonding electrons to the  level
resulting in activation of the alkene molecule, which tends to undergo a wide
variety of reactions, many of which are of great industrial importance. Some
typical examples involving metal – alkene intermediates in the homogeneous
catalyzed organic synthesis are illustrated as follows:
(h) Hytdrogenation:

(i) Hydrosilylation:

220
(j) Carboxylation:

(k) Hydroformylation:

(l) Oligomerisation:

(m) Isomerisation:

221
(n) Dismutation:

6.4.5 Reactions of Coordinated Alkynes

As expected, the reactivity of coordinated alkynes would be to some


extent influenced by the nature of the metal involved. Thus alkyne complexes
of transition metals in low oxidation states generally undergo reactions with
electrophiles, while complexes of transition metals in higher oxidation states as
well as cationic complexes are usually reactive towards nucleophilic moieties.
A few examples of these types of behaviour are illustrated below:

(a) Displacement reactions


The displacement of one alkyne by another has been exploited for the
preparation of new alkyne complexes:

Pt ( PR3 ) 2 ( HC  CH )  RC  CH  Pt ( PR3 ) 2 ( RC  CH )  HC  CH

In these reactions the case of alkynes displacement can be represented as:


acetylene < alkylacetylenes < arylacetylenes < nitroacetylenes

The following two reactions represent two types of displacements from

222
alkyne complexes with reagents other than alkynes:

Pt ( PPh3 ) 2 (CH  CH )  2 PPh3  Pt ( PPh3 ) 4  HC  CH


(excess )

[ PtCl (en)( HC  CH )] Cl 


PtCl 3 ( HC  CH )  en THF

Reaction on double bond of coordinated alkene:

(ii) Alkyne complexes also undergo a number of other interesting reactions,


involving, for example, oligomerization and hydrometallation, e.g.:

CO
RC  CH  [ RC  C  Pd ] 
Pd ( II )
 RC  CCO2 R
11

R' OH

Ni (CO) 4
HC  CH  H 2 O      H 2 C  CHCO2 H
0
150 C , 130 atm

PdCl 2 / thiourea
HC  CH  CO  MeOH     MeO2 CCH  CHCO2 Me
O2

(d) Reactions with Nucleophiles:

In these reactions the nucleophilic reagent reacts with metal in Cis-form


or with proton of alkyne in trans form:

223
(e) Reaction with Electrophilies:

HCl
(i) Pt(PPh3)2 (2 Ph C  C Ph)  Pt(PPh3) Cl2 + Ph' CH = CH Ph

6.4.6 Reactions of Coordinated Allyls

The important reactions of 3-allyl complexes are (a) Insertion, (b) Metal
exchange, (c) Halide exchange, (d) Displacement and (e) Nucleopuilic
reactions:
(a) Insertion reaction :
Cl

2[ Pt ( PPh3 ) 2 (  C 3 H 5 )] Cl  2CO  ( Ph3 P) 2 Pt
3   CHCl3


COCH  CH CH 3 (Cis and trans)

224
(b) Metal exchange reaction :

[{Pd X ( 3  C3 H5 )}2 ]  2Hg  2 Pd  Hg ( 3  C3 H5 )  Hg X 2

[{Pd X ( 3  C3 H5 )}2 ] [Co(CO)4 ] [Co (CO)2 ( 3  C3 H5 )] Co(CO)2 ( PPh3 ) ( 3  C3 H5 )


PPh 3

(c) Exchange reaction :

Pt ( 3  2  Me C3 H 4 )2  2E Ph3  Pt ( EPh3 )2 (1  C3 H5 ) ( 5  C5 H5 )

Cr ( 3  C3 H5 )3  6 PF3 Cr ( PF3 )6

Co (CO)3 ( 3  C3 H5 )  NO  Co (CO)3 ( NO)

(d) Halide Exchange

[{Pd (  x) ( 3  C3 H5 )}2 ]  2 Tl  C5 H5  2 Pd ( 3  C3 H5 )( 3  C3 H5 )  TIX

(e) Nucleophilic affack

(i) on metal :

225
(ii) On ferminal C-atom of allyl group :

6.4.7 Reactions of Coordinated Dienes

The important reactions of butadiene are: 1. Substitution, 2. Nucleophilic


addition 3. Electrophilic addition and 4. Reactions of substituents in ligand.

a) Substitution Reactions:
In these reactions diene ligand is nucleophilically substituted.
Fe (4-C4H6) (CO)3 + 2PPh3  Fe (CO)3 (PPh3)2 + C4H6

b) Nucleophilic addition:
In these reactions due to nucleophilic reaction of H-, R-, CN-, MeO-, R3N
etc. (Nucleophilies) on carbon of oleffins, diene ligand or any other
ligand is displaced or addition on carbon taken place:

226
c) Electrophilic addition

In these reactions there is addition of proton or eliminatation of proton:

d) Reaction of substituent groups:

6.4.8 Reactions of Coordinated Cyclobutadiene

Cyclobutadiene appears to be too labile for independent existence, thus, when


released from their captive traps (combinations with transition metals), these
highly reactive molecules rapidly decompose, dimerize or isomerize or react
with suitable organic substrates to generate new novel organic products:

227
Other reactions are decomposition and dimerisation, or isomerisation
giving novel products:

228
Dewar Benzene

6.4.9 Reactions of Coor5dinated Cyclopentadiene


Cyclopentadienyl complexes are covalent compounds. These are stable not only
for oxidation, but also thermodynamically. Some specific reactions are given
below:
1. Aromatic Properties

229
2.
Protonation of metal
(iv) Fe (5-C5H5)2 H+ [FeH(5-C5H5)]

(v) ReH (5-C5H5)2 H+ [ReH2(5-C5H5)]+

(vi) MoH2 (5-C5H5)2 H+ [MoH3 (5-C5H5)2]+

3. In these (5 – C5H5) is transfered to other metal


(iv) M (5-C5H5)2 + Fe Cl2  Fe (5-C5H5)] + MCl2 (M=Cr, Mo, V, Mn)

(v) Ni (5-C5H5)2 + Fe (CO)5  [(5-C5H5) Ni (CO)2 Fe (CO)(5-C5H5) +


2CO

(vi) Ni (5-C5H5)2 + Ni (CO)4 2[Ni (CO)(5-C5H5)2] + 2CO

230
6. Reduction Reaction
Metal atom or / and cyclopentadienyl group is reduced
(iii) Co+ (5-C5H5)2 + Na BH4 Co (5C5H5) (4-C4H6)
C2H2NH2
(iv) Fe (5-C5H5)2 + Li Fe + 2 C5H5-

5. Addition reaction

231
6.4.10 Reactions of Coordinated Arenes
Unlike the cyclopentadienyl group, arene ligands are readily displaced
from complexes by other neutral ligands, such as carbon monoxide, phosphines,
2, 2' – bipyridyl, etc. Some important reactions are as follows:

6. Arene displacement reaction


Cr( 6  C6 H6 )2  C6 H5 H3  3CO 
nkc
Cr(CO)3 ( 6  C6 H5CH3 )  C6 H6

1000 C
Mo( 6  C6 H 6 )3  6 PF3  Mo ( PF3 ) 6  2C6 H 6
600 Air

7. Reaction with arene ligand

Arene complexes give substitution and addition reactions with weak


nucleophilic reagents like H-, R-, MeO-, R3N etc.
( 6  C6 H 6 ) 2 Cr  MeO  ( 6  C6 H 6  OMe)  Cr ( 6  C6 H 6 )

( 6  C6 H 6 ) 2 Re   H   ( 6  C6 H 6 )  Cr ( 6  C6 H 7 )

lkbDyksgsDlsu
(  C6 H 6 ) 2 Cr   Li Bu   ( 6  C6 H 6  Li)  Cr  ( 6  C6 H 6  Li)
6

700 C

Due to metallation with lithium, the product can be used for many
organic synthesis:

8. Redistribution:
Cr ( 6  C6 H 6 ) 2  Cr (CO) 6  Cr (CO)3 ( 6  C6 H 6 )

9. Redox reaction:1

2 Cr ( 6  C6 H 6 )2  O2  2H 2O    2[Cr ( 6  C6 H 6 )2 ] OH 
Na2 S 2 O4

232
10. Friedel – Craft Acylation
CH 3COCl
(  C6 H 6 ) 2 M       ( 6  C6 H 6 )  M   ( 6  C6 H 5CH 3 )( M  Cr , Mn)
6

AlCl 3 rFkk ty vi?kVu

Amongst mixed complexes arene – carbonyl complexes are important.


These may be prepared by replacement of CO from metal carbonyls.

Cr (CO)6  C6 H 6  (C6 H 6 ) Cr (CO)3  3CO

These complexes are more reactive compared to corresponding bis


are3nes. They also follow. EAN rule (Fig. 4.16)

CR

C C C
O O O
Fig. 4.16

CHECK YOUR PROGRESS – 2

Notes : (1) Write your answers in the open space given below.
(2) Compare your answers with those given at end of the unit.
(a) (i) Two important reactions of coordinated alkenes, resulting in new
alkenes are :

(x) ............................................

(y) ............................................

233
(ii) The ease of substitution of alkynes is .....................< .......................
<................ <.................

(iii) Reaction of coordinated alkynes with nucleophilic reagents give


..................................................

(iv) Insertion of CO2 and elimination of nickel in Ni (3 – C3H5) gives


....................................................

(b) (i) Addition reaction of coordinated dienes are :

(x) .....................................

(y) .....................................

(ii) cyclobutadiene tricarbonyl iron (II) on reaction with .......................


gives ...........................

(iii) Formation of .................................... derivative due to reaction of


cyclopentadienyl complex with ethene in presence of AlCl 3 is an
example of ........................................ property. While, transfer
of .................................. group on other metal as a result of its
reaction with metal salt is ..................................... reaction.

(iv) Coordinated arenes give many aromatic reactions the important


ones are :

(x) .............................. displacement reaction

(y) ............................. reaction.

234
6.5 LET US SUM UP

After going through this unit you would have achieved the objectives
stated earlier. Let us recall what we have discussed :

 The simplest definition of a catalyst is a species which facilitates a


particular reaction without being consumed in the process; it may be
regenerated in its original form, but some times in a lower or a higher
oxidation state.

 A catalyst is that it lowers the activation energy barrier for a


thermodynamically allowed (but kinetically slow) reaction resulting in an
enhancement of the rate of the process. The efficiency of a catalyst is
often expressed in terms of turnover frequency.

 In addition to the novel role of organotransition metal being continuously


made in the application of these organometallics especially as
"stoichiometric reagents". The main distinguishing feature between
catalytic and stoichiometric reagents used as initiators in synthetic
procedure, is that the latter are generally not regenerated.

 Coordinated alkylidenes show strong nucleophilic properties. The


important properties of these compounds may be divided into three
groups :

(a) Reactions of nucleophilic carbon.

(b) Reactions of unsaturated carbon.

(c) Decomposition reactions.

235
 Organo – copper, especially lithium dimethyl cuprate has been proved an
important reagent in organic synthesis. Its important reactions are :

(i) Halogen Substitution,

(ii) Conjugated addition,

(iii) Alkylation of allylacetate or epoxides, and

(iv) Formation of acids from acid chlorides.

 Coordinated alkylidynes are used as catalyst in organic synthesis. Its


important reactions are : (i) In the Synthesis of new alkynes and (ii)
Insertion reactions.

 Coordinated Carbene, in complexes, behaves as a nucleophilic, while


carbene-carbon due to its electrophilic behaviour give different reactions
to give new products.

 In coordinated alkenes, alkene is a weak ligand, which is easily


substituted by strong ligands like cyanide, tert. phosphines etc.

After coordination alkene molecule becomes active and takes part in


different types of reactions to give different new products. Its important
reactions are :

(i) Nucleophilic Substitution reactions,

(i) Homogenous catalysis reactions, e.g. hydrogenation, hydrosilation,


carboxylation, hydroformylation, oligomerisation, isomerisation
and dismutation.

236
 Coordinated alkynes react with both nucelophilic and electrophilic
reagents. When they are coordinated with metals in their lower oxidation
state, they react with electrophiles; but when they are coordinated with
metals in their higher oxidation states they react with nucleophilic
reagents.

 The important reactions of coordinated allyls are : (i) Insertion (ii) Metal
– exchange, (iii) Halide exchange, (iv) displacement and (v) Nucelophilic
reactions.

 Coordinated butadienes and cyclobutadienes play important part in


organic synthesis. Many substitution reactions give new products.

 The important reactions of coordinated cyclopentadienyl are their


aromatic properties, fission reactions, addition reactions and reduction
reactions.

 Similarly the important reactions of coordinated arenes are their aromatic


properties, which give new products in organic synthesis.

6.6 CHECK YOUR PROGRESS : THE KEY

1(a) (i) low energy


increase of
turnover efficiency

(ii) (x) Reactions of nuclophilic carbon


(y) Reactions with unsaturated compounds
(z) Decomposition reactions.

237
(iii) 1, 9 dimethyl p-quinone acetate

(iv) (x) Vinyl ether


(y) Cyclopropene

(v) ester

(vi) carbene ligand


new alkene

2(a) (i) (x) oligomerisation

(y) dismutation

(ii) Acetylene < alkylacetylene < arene acetylene < nitro acetylene

(iii) substituted alkene

(iv)  - lactone

(b) (i) (x) nucleophilic


(y) electrophilic

(ii) Ce4+
Cubane

(iii) ethyl
aromatic
(5-C5H5)
fission
(iv) arene
Fridel - Craft

238
M.SC. (FINAL) CHEMISTRY

PAPER –IV : ORGANOTRANSITION METAL CHEMISTRY

BLOCK-III

Unit -7 : Homogenous Catalysis - II

Unit-8 : Fluxional Organometallic Compounds

Author – Dr. Purushottam B. Chakrawarti


Editor – Dr. Anuradha Mishra

239
M.Sc (Final) CHEMISTRY
Paper-4: ORGANOTRANSIONAL METAL
Block-III : Summary

This block includes two units, unit-7 and-8

Unit-7: Homogeneous catalytic properties of transition metal


organometallics, describes the importance of organotransition
metal complexes as catalysts in different industrially important
reactions. It also explains mechanisms of Zeigler-Natta, Wacker
processes and petroleum synthesis.

Unit-8: Fluxional Organometallic Compounds, registers an analysis of


different transition metal organometallic compounds for their
fluxional behaviour, eg olefins, alenes, cycloalkenes, allyls and
dienyl complexes.

240
UNIT – 7 HOMOGENEOUS CATALYSIS – II : HOMOGENEOUS
CATALITIC PROPERTIES OF TRANSITION METAL
ORGANOMETLLICS

Structure

7.1 Introduction

7.2 Objectives

7.3 Homogeneous Catalytic Properties of Transition Metal Organometallic


Compounds.

7.3.1. Oxidative Additions

7.3.2. Insertion and Elimination

7.3.3. Nucleophillic Addition of Coordinated Ligands

7.4 Some Homogeneous Catalytic Reactions of Industrial Importance.

7.4.1. Hydrogenation of Alkene

7.4.2. Zeigler Natta Polymerisation of Olefins

7.4.3. Hydroformylation of Alkene

7.4.4. Wacker Process i.e. Oxopalladation.

7.4.5. Synthetic Gasoline

7.5 Let us sum up

7.6 Check your progress : The key.

241
7.1 INTRODUCTION

In addition to variety of synthetic applications of some typical main


group organometallic reagents transition metals and their organometallic
derivatives are also finding extensive applications in a large number of
industrially and biologically important processes. For example, the well-known
Haber process for synthesis of ammonia involves an iron/iron oxide catalyst;
the oxidation of ammonia (a process used in the manufacture of nitric acid) is
catalyzed by a Pt/Rh catalyst, and the hydrogenation of vegetable oils to solid
fats is based on Raney (finely divided) nickel as catalyst.

Although the role of organometallic catalysts in the biologically


important enzymatic reactions is being recognized more and more, our main
endeavour in this chapter would be to concentrate around rather simpler
synthetic catalytic procedures which are known or have been postulated to
proceed via metal-carbon bond-making and/or breaking pathways.

7.2 OBJECTIVES

The main aim of this unit is to discuss the importance of organotransition


metal complexes as catalysts in different industrially important reactions. After
going through this unit you will be able to :

 discuss the reactions taking part in the mechanism of catalytic reactions


of organotransition metal complexes, such as oxidative addition,
insertion and elimination and nucleophilic addition of ligands,

 describing hydrogenation, polymerisation and hydroformilation etc


reactions, can discuss the mechanism of catalytic part played by

242
organotransition metal complexes in industrially important reactions, and

 discuss the mechanisms of Zeiglar – Natta, Wacker process and synthesis


of petroleum process.

7.3 HOMOGENEOUS CATALYTIC PROPERTIES OF ORGANO


TRANSITION METAL COMPOUNDS

Contrary to the applications of main group organometallics (which are


generally stoichiometric in nature), an increasing amount of evidence shows
that synthetic procedures involving transition metal organometallics are more
often catalytic in nature.

The variety of reactions catalyzed by transition metal organometallics is


quite large and these can be grouped in slighly different patterns. In the
following sub-sections, an attempt would be made to indicate the specific type
of interactions in selected catalytic processes described below under different
headings, the first five of which are examples of essentially homogeneous
catalysis and the last five deal with homogeneous/ heterogeneous processes.

From practical point of view homogeneous catalysis is also important as


it gives required product selectively. In industrial production processes,
homogeneous catalyst is selected for exothermic reactions as it is easy to cool
down the solution during the process.

During catalysis cycle following steps are very important:

(i) Reaction with organic reagent (Oxidative addition)

(ii) Reaction of coordinated ligand, and

(iii) Elimination of product.

243
The important processes used in these steps are given below:
7.3.1 Oxidative Addition

Oxidative addition (or oxad) reaction which are useful for establishment
of new transition metal-carbon -bonds involve the oxidation (i.e., increase in
the formal oxidation number), accompanied by an increase in the coordination
number of the central metal atom. Complexes of metals in low spin d7, d8, or d10
configurations generally undergo this type of reaction and in the process of
enhancing their coordination number, the central metal tends to attain the stable
closed-shell configuration corresponding to 18 valence electrons.

Coordinative unsaturated state of the central transition metal appears to


facilitate an 'oxad' type of reaction. For example, in the following reaction,
iridium (I) changes from 4-coordinate 16-electron to 18-electron iridium (III):

IrCl(CO)(PPh3)2 + CH3I Ir(CH3) (CI)(I)(CO)(PPh3)2

Similarly, in the following reaction, 5-coordinate 18-electron ruthenium


(0) is converted into 6-coordinate 18-electron ruthenium (II), accompanied by
the loss of a CO molecule:

Ru(CO)3(PPh3)2 + CH3I Ru(CH3)(I)(CO)2(PPh3)2 + CO

To facilitate oxidative addition type of reactions, the metals should


preferably by in low oxidation state. Unlike the main group metals (e.g. the
formation of Grignard reagents from metallic magnesium and alkyl halides), the
transition metals themselves are not generally reactive enough under ambient
conditions and have to be in low oxidation state in the presence of coordinated
ligands.

244
The oxidative addition reactions have assumed special importance in
catalytic processes and this is generally the initiating step in a catalytic process
and involves the formation of bonding of some kind (,  other delocalized
type) between the transition metal and the organic/inorganic substrate (through
oxidative addition or coordination); this is generally a key step in the catalytic
or / and stoichiometric process, e.g.:

The oxidative addition/ coordination reaction of a ligand is generally


facilitated by the availability of vacant coordination site (s) on a metal complex
in solution (homogeneous catalysis) or a metal surface (heterogeneous
catalysis). The coordinative unsaturation may also arise from the dissociation of
loosely held solvent molecules, giving rise to potentially vacant site(s). For
example, a square planar d8 (4-coordinate) complex such as RhCl(PPH3)3
(known as Wilkinson's catalyst) is coordinatively unsaturated and is one of the

245
most active and versatile catalysts known so far. In this connection, it may be
noted that coordinative unsaturation is generally guided by the 18-electron rule
(or effective atomic number rule). For example, metal complexes with 18
electrons in the valence shall are coordinatively saturated, irrespective of
coordination number, and therefore catalytically ineffective, e.g.,
IrCl(H)2(PPh3)3(d6), Fe(CO)5(d8), etc., whereas species with 16 electrons or less,
such as RhCl(PPh3)3 are coordinatively unsaturated.

For coordinatively unsaturated species (e.g. d8 species) in solution,


coordinating solvent molecules occupying the vacant sites could be displaced
by reacting molecules:

These coordinated solvent molecules (and even some of the co-ligands)


should be too tightly bound with the metal atom, otherwise they effectively
poison the catalyst which is unable to present a vacant coordination site for the
incoming substrate molecule.

In five coordinated (d8) metal complexes, vacant sites can also arise by
dissociation of one or more ligands either thermally or photochemically e.g.,
(-PPh3, heat) (-PPh3)
RhH(CO)(PPh3)3 RhH(CO)(PPh3)2 RhH(CO)(PPh3)

The oxidative addition reactions of organometallic compounds are of


great utility in the synthesis of novel and interesting types of compounds;
oxidative addition of alkyl halides to transition metal complexes, designated by

246
the following equation, hqas been extensively studied in view of it involvement
in catalytic reactions:

Mln + RX  M (R) (X) Ln

For example, the addition of methyl iodide to the rhodium (I) complex,
RhI2 (CO)2 is a key step in the Monsanto acetic acid synthesis; in the initiating
reaction rhodium is oxidized from + 1 to + 3 oxidation state:

In view of the extensive applicability of oxidative addition reactions in


catalysis, some of their essential features are indicated as follows:

(A) Low Oxidation State of the Metal


As oxidative addition reaction can be treated as a process undergoing loss of
electrons from the electron rich metal centres, the same should be facilitated by
the metal atom in the complex being in the lower oxidation state; in fact, any
change in the metal complex which enhances the electron density at the central
metal leads to an increase in reactivity. Although theoretically metal atoms in
metallic (or zero oxidation) state could be expected to be better precursors for
such reactions, yet these are of only very limited applicability on energetic

247
grounds. However, the development of metal vapour and reactive metal
production techniques have added new dimensions in this particular area.

(B) Coordinative Unsaturation


The oxidative addition reactions are generally accompanied by an increase in
the coordination number of the central metal atom. It is, therefore, expected that
organometallic precursors should be coordinatively unsaturated, e.g.
IrCl(CO)(PPh3)2; (RhCl(PPh3)3, etc. The coordinative unsaturation can be
achieved either (i) by the generation of a vacant coordination site or (ii) by the
ability of a complex to exit in different coordination numbers.

(C) Nature of the Metal


There are many indications that the lighter metals in a given sub-group are less
basic or nucleophilic than the heavier elements. For example, while the
complex IrCI(CO)(PPh3)2 (Vaska's compound) reacts completely and
irreversibly with CH3I:

With a few exceptions, the general tendency to undergo oxidative


additions parallels the trends indicated below for the Group VIII metals:

Fe(O) Co(I) Ni(II) Increasing tendency


for oxidative addition
Ru(O) Rh(I) Pd(II) reactions
Os(O) Ir(I) Pt(II)

Increasing tendency for oxidative addition reactions

248
(d) Electronic nature of the Ancilliary Ligands
The presence of ancilliary ligands which enhance the electron density around
the metal atom in a complex also influences the course of the reactions. For
example, RhCI(PPh3)3 undergoes facile oxidative addition, but RhCI(CO)
(PPh3)2 is much less active for oxidative addition. The replacement of one
strongly donor and weakly acceptor PPh3 ligand in RhCl (PPh3)3 by a weakly
donor and strongly acceptor CO ligand should result in a lower electron density
on the central rhodium atom in the latter complex, RhCI(CO) (PPh 3)2 and thus
explain the difference in reactivity of the two complexes, although a steric
factor is another parameter to be considered. In a series of isosteric triaryl-
phosphines in the Wilkinson complex, the observed order of hydrogenation
activity: (p-CH3OC6H4)3P > (C6H5)3P > (p-FC6H4)3P can be explained on the
basis of the variation in the donor capability of the three ligands.

(E) Nature of the Addendum


The formation of metal – carbon bond by the oxidative addition of
heteronuclear organic substrates such as organic halides is of wide applicability.
Oxidative addition reactions involving cleavage of carbon-carbon bond would
obviously be much less feasible both on thermodynamic as well as kinetic
considerations. However, such cleavage reactions can be brought about under
special conditions. For example, sterically crowded addend such as
hexaphenylethane are cleaved as it results in the release of a large strain in
C2Ph6 molecule:

249
Alternatively, electronic activation of carbon-carbon bonds in molecules
like dimethyloxalate and cyanogen can facilitate the cleavage reactions:

(F) Stereochemistry and Mechanism of Oxidative Addition Reactions

A detailed study of the stereochemistry of the product of oxidative


addition reactions by physico-chemical techniques such as n.m.r. and i.r.
spectroscopy has often provided a valuable insight in the mechanism of such
reactions.

For example, the addition of CH3I to IrCI(CO)(PMePh2)2 can


theoretically yield nine possible stereoisomers.

7.3.2 Insertion and Elimination

(a) Insertion:

These reactions are of great significance in catalytic processes.


Unsaturated molecules such as carbon monoxidre, isocyanides and sulphur
dioxide undergo insertion into the metal – carbon bonds, producing new and
often, exciting derivatives.

250
(i) Insertion of carbon monoxide. The CO insertion products are especially
important, as they appear to be key intermediates in a variety of catalytic
and industrial processes, such as hydroformylation reaction:

In view of the high oxgen affinity of early transition metals, lanthanides


as well as actinides, their alklys gives 2- acyls and other nonclassical types of
CO insertion products; this oxophilicity results in dihapto oxgen bound
migratory insertion products A and B :

as haloalkyls of group 4 transition metals and of the actinides, MR 2 (5-C5H5)2


and MRX (5-C5H5)2; one of these isomers has C – O vector pointing away
from the additional ligand X(C) and the other one depicts the opposite C-O
orientation (D). Acyl derivatives of group 4 metals, such as Ti(COCH3)CI(5-
C5H5)2 and Zr(COCH3)(CH3) (5-C5H5)2 show structures of types (D). By
contract, the actinide analogues favour structure (C) or at least (C can be as
stable as (D) :

251
(Where Cp=(5-5H5)

A few typical example of 2- acyl and nonclassical type of


CO insertion are shown below:

(Cp*=(5-C5Me5)

252
Another interesting feature of carbon monoxide insertion is the regio-
selectivity which is observed when two different hydrocarbyls are present, as
for example, in ZrRR'(5-C5H5)2 (where R/R' = CH(SiMe3)2/Me, Ph/Me,
CH2SiMe3/CHPh2):

(5-C5H5)2 ZrMe{CH(SiMe3)} + CO

 (5-C5H5)2 ZrMe{2-COCH(SiMe3)2}

(5-C5H5)2ZrMePh + CO  (5-C5H5)2 Zr{2-COMe}Ph

(5-C5H5)2ZrRR' + CO  (5-C5H5)2 Zr(2-COR)R'

(R = Me, CH2SiMe3; R' = CHPh2)

The mechanism of insertion of carbon monoxide into the metal – carbon


bond has been the subject of a large number of penetrating studies, e.g., that of
MnCH3(CO)5 with 14CO. The main conclusions from these may be summarized
as follow:

As shown in the following step,

The CO molecule which assumes acyl character is not the external one, but it is
one of the CO groups already coordinated to the metal. Interstingly, the
incoming CO molecule occupies a position 'cis' to the acyl group.

In order to explain these observations, it can be assumed that the primary

253
step consists in the following type of conversion:

The above equilibrium would obviously be facilitated by a donor solvent 'S'


resulting in the formation of Mn (COCH3) (CO)4 (S) :

Mn (COCH3) (CO)4 + S Mn (COCH3) (CO)4 (S)

The hexacoordinated species on the right in the above equation would


interact not only with an incoming 'CO' molecule but also with another donor
ligand (L) like phosphines :

(ii) Insertion of carbon dioxide, carbon disulphide and sulphur dioxide

Possible modes of insertion of CX2 (i.e. CO2 or CS2) and SO2 in


transition metal-carbon bonds are represented below:

254
A few typical examples of such insertion reactions are given below :

Insertion modes of CO2 into Cu – R bonds are generally dependent on the


nature of the supporting ligands attached with the metal centre, e.g.:

255
Although products from SO2 insertion into transition metal-carbon
bonds can also vary, yet the usual product is S-sulphinate:

M – R + SO2  M(SO2R)

Some typical examples of SO2 insertions leading to the formation of S-


sulphinate derivatives are illustrated by the following reactions:

 78 0 C
TiMe ( 5 - C H )  2SO     Ti (1  O SMe) ( 5  C H )
5 5 2 2 2 2 5 5 2
O  bonded

MR(CO) 5  SO2  Mn( 1  SO2 R) (CO) 5

(R =Me, Et, Ph, CH2Ph) S-bounded


FeMe(CO) 2 ( 5  C5 H 5 )  SO2  Fe( 1  SO2 Me) (CO) 2 ( 5  C5 H 5 )

NiMe( PBu 3 )( 5  C5 H 5 )  SO2  Ni( 1  SO2 Me) ( PBu 3 ) ( 5  C5 H 5 )

AuMe(PMe3) + SO2  Au (1- SO2Me)(PMe3)

AuMe3 (PMe3) + SO2  cis – AuMe2 (SO2Me)(PMe3)

AuMe2 Ph (PMe3) + SO2  Au(SO2Me)(Me)(Ph)(PMe3)

The selective insertion of SO2 into a gold methyl rather than a gold

256
phenyl bond in the last reaction indicates that SO2 does not act as a simple
electrophilic reagent. Rather coordination of SO2 to gold followed by alkyl
transfer is considered more plausible.

Several different mechanisms are possible for SO2 insertion into a


metalcarbon bond; one of these involving exo attack, is illustrated below:

By contrast, SO2 insertion into the Co-R groups of cobaloximes, has been
explained, on the basis of a radical chain mechanism:

Co – R  Co0 + R0

Co0 + SO2  CoSO02

CoSO02 + Co – R  CoSO2R + Co0

Some illustrative examples of CS2 insertion into transition metal – carbon


bonds are the following :

MnR(CO)5 + CS2  Mn(2 – S2CR)(CO)4 + CO

( R = Me, Ph, p-Tol)

257
(iii) Insertion of isocyanides (RNC): Although isocyanides are isoelectronic
with CO, yet examples of their insertions into the transition metal – carbon
bond are relatively fewer in number. Few examples of isocyanides insertion
reactions are:

(R = Me, Ph, o – C6H4Me)

(5 – C5H5)2ZrRR' + R" NC  (5 – C5H5)2 ZrR (5 – C5H5)2

In contrast to CO insertion in the above system, the insertion of an isocyanide


R" NC into the more hindered (R') of the two R and R' hydrocarbyl groups
under ambient conditions appears to be more general.

(iv) Insertion of unsaturated system into metal – metal bond :

Co2 (CO)8 + C2F4  (OC)4 Co – CF2 CF2 – Co(CO)4

Me3Sn – Mn(CO)5 + C2F4  Mn (CF2CF2SnMe3)

(v) Insertion of unsaturated compounds into M – C bonds:

MnCH3 (CO)5 + CO  Mn {C(: O)CH3} (CO)5

MnPh(CO)5 + PPh3  Mn {C: O}Ph} (CO)4 (PPh3)

trans – PtCl(CH3)(PEt3)2 + CO  trans – Pt (C(:OCH3) Cl (PEt3)2

258
b) Elimination:

These reactions in most cases are the reverse of insertion reactions. As the name
signifies, this class of reactions involves elimination of a molecular species
from appropriate complexes with or without change of oxidation state of the
central metal atom. The former type is accompanied with a lowering of the
oxidation state of generally an intermediates species involved in catalytic
processes. The latter type, involving elimination of molecules like N2, CO, CO2,
SO2 and H2 from appropriate species such as azoderivatives, acyls, carboxylates,
sulphinates and hydrides respectively, leads to the formation of a new transition
metal-carbon -bond as illustrated by the following typical examples:

(i) Azo-derivatives :

trans  PtCl ( N  N  C6 H 4NO 2  P)( PEt 3 ) 2 120


 
0
C

trans  Pt Cl (C6 H 4 NO2  p ) ( PEt 3 ) 2  N 2

(ii) Acyls :

Mn(COC6 H 4 Me  p) (CO) 5 


hv
Mn(C6 H 4 Me  p) (CO) 5  CO

80 0 C CH2
(OC) 5 Mn  CH 2  CH  CH 2 HC  Mn(CO) 4  CO
or hv CH2

Fe(COPh)(CO) 2 ( 5  C5 H 5 ) 
hv
Mn( Ph)(CO) 2 ( 5  C5 H 5 )  CO

Li  [CO(CO) 4 ]  F3CCOCI  Co(COCF3 )(CO) 4  LiCl

  250 C
Co(CF3 )(CO) 4  CO

259
(iii) Carboxylates

Ni(CO2 Ph) 2 (bipy ) heat



 NiPh2 (bipy )  CO2

K 2 PtCl 4  2TlO2 CC6 F5  2 py heat



 trans  Pt (C6 F5 ) 2 ( Py ) 2
 2 KCl  2TlCl  2CO2

(iv) Sulphinates

Fe(SO2 R)(CO) 2 ( 5  C5 H 5 ) heat


 FeR (CO) 2 ( 5  C5 H 5 )  SO2


IrCl2 (SO2C6 H 4 Me  p)(CO)( PPh3 ) 2

heat

 IrCl2 (C6 H 4 Me  p)(CO)( PPh3 ) 2  SO2

Pt (SO2 Ph)(Cl ( PR3 ) 2 ) heat



 PtCl ( Ph)( PR3 ) 2  SO2

(v) Hydrides

(vi) Elimination of an alkene and proton abstraction. One such reaction


pathway is the so-called β-elimination of alkene with concomitant formation of
the metal hydride.

260
Some typical examples of alkene elimination reactions are illustrated below:

Reagents such as {Ph3C}+{BF4}- tend to abstract a proton form β-


hydrogen containing hydrocarbyl group attached to the transition metal and the
olefin thus generated sometimes remains coordinated to the meal, e.g..

7.3.3 Nucleophilic Addition of Coordinated Ligands

Many important reactions of nucleophilic additions have been given in


units -2 and -3. Similarly; nucleophilic additions on coordinated carbon
monoxide have also been studied in detail:

M-C≡O+Nu- [M-C(Nu) O] –

Generally, Coordinated unsaturated hydrocarbons are specially sensitive for


nucleophilic addition. Although in free state they do not take part in these
reactions, but in coordinated state, due to shift of electron density, they become
sensitive for these reactions.

261
Chemisorptions of hydrogen on platinum metal and coordination of hydrogen in
iridium complex are also important.

As has been pointed out H2 molecule can co-ordinate with metal complexes
without breaking of H-H bond, eg. in [W (CO)3 (H2) (P'Pr3)2]. Now large
number of such compounds has been prepared. They may regard processors of
hydride complexes. MOT indicates that electron-density from H2 molecule is
transferred into vacant orbital of the metal. Simultaneously back bonding in -*
orbital of H2 takes place. Similar reactions may take with C-H and C-C bonds
e.g. intramolecular cyclometallation or orthometallation reactions of

262
coordinated PPh3 :

Ph P

(Ph3 P)3 Ir Cl  (Ph3 P)2 Ir


H
Similarly, C-H bond coordinates with metal in complexes. Brown and
associates, using neutron diffraction methods confirmed formation of CH – Fe

bond in [Fe (n3-C8H13)] [P(OMe3)3] Similarly Calvert and shaple, confirmed


formation of C-C-Os bonding in triosmium complex.

This type of coordination of CH bond has been designated as Agnostic


interaction)

Trans-disubstituted derivative also show coordination into transition


metal complexes. [HFe (CO)4]- +2PR3 BuOH trans. (CO)3 Fe (PR3)2.

A number of reactions of industrial importance show intermolecular


combination. For example in petroleum industry use of Ir-complex as a catalyst
also involves intermolecular addition during the mechanism.

263
Check your Progress-1

Notes: (i) Write your answers in the space given below.


(ii) Compare your answers with those given at the end of the
unit.

A (i) The important processes involve in homogeneous catalysis


reactions of industrial productions are;
(x) ......................
(y) .......................
(z) ...................
(ii) The reverse reaction of insertion is ........... while oxidative addition
is the .............. of catalysis process, in which ........... between
transition metal and................ takes place.
(iii) For oxidative addition it is necessary that there are vacant..... in
...........and ........... are available for bonding.
B (i) Insertions are those reactions, in which ........... of ...... is not
changed and inserted radical is linked in between..........
(ii) Important examples of insertion reactions are
(x) ......................
(y) .......................
(z) ...................
(iii) Generally coordinated................. are ...... towards nucleophilic
addition. In free state they....... take part in these reactions, but in
coordinated state due to ................ they become very ..... for these
reactions.

264
7.4 SOME HOMOGENEOUS CATALYTIC REACTINOS OF
INDUSTRIAL IMPORATNCE

7.4.1. Hydrogenation of Alkenes (Wilkinson's Catalyst)

Although the reaction;

H2C=CH2 +H2 H3C –CH3

is highly exothermic ( HO +136.8 kJ/mole) ethane (ethylene)does not react with


hydrogen at an appreciable rate without an appropriate catalyst; the high
activation energy corresponds to negligibly slow reaction rate.
The uncatalyzed hydrogenation of alkenes could theoretically occur by
conceptually simple, "four-centre" mechanism (path 'p' in scheme) or a stepwise
process (path 'p').
However, both the paths are unfavorable, the concerted path ('p') is
"forbidden" by the Woodward-Hoffman orbital symmetry rules i.e. electron
can not flow from hydrogen (H2) to the empty * orbital of ethane as there is no
net overlap, whereas the stepwise process (p I') would necessarily involve high
energy hydrogen atoms.

However, a large number of transition metal ions of electronic


configurations varying from d5 to d10 {Ru(III)d5, Ru(II)d6, Co(II)d7, Co(I)d8,R
h(I)d8, Ir(I)d8, Pd(II)d8, Pt(II)d8, Ag(II)d9, Cu(I)d10, Ag(I)d10} are known to
promote the above hydrogenation reaction by lowering the activation energy
barrier for the process. The d-orbitals of a transition metal have the correct
symmetry to interact directly with hydrogen molecule, the flow of electrons
from the filled metal d-orbitals into the anitbonding molecular hydrogen orbital
causes H-H bond dissociation and leads to the formation of two metal-hydride
bonds. The hydrogen atoms can now be transferred to the alkene.

265
The hydrogenation of naturally occurring materials/products (general or
at selected specific sites of unsaturation) with double bonds often leads to very
useful materials. In this direction, hydrogenation of vegetable oils to solid facts
can be cited as an important example. These hydrogenation reactions are
assuming ever-increasing importance due to their newer and novel applications
in petrochemical and drug industries. In these directions, useful heterogeneous
catalysts for specific purposes are Adams catalyst (platinum black oxide):Pd/C'.
Pd/BaSO4, Raney nickel, rhodium, ruthenium, and copper-chromium
oxide.Typical hydrogenations (using heterogeneous catalysts) have to be carried
out at moderately high pressures of hydrogen (~1000/psi) and generally at
elevated temperatures. Any catalysts capable of facilitating hydrogenation
reactions at ambient conditions, therefore, are obviously very attractive
propositions and in more recent years, homogeneous catalytic systems have
proved highly successful in these directions.

Fig. 7.1

266
Out of a large number of homogeneous hydrogenation catalysts or
catalyst precursors such as RhCI(PPh3)3; RhH(CO)(PPh3)2; IrCI(CO)(PPh3)2;
RuHCI (PPh3)3; Ru (H) (CI) (CO) (PPh3)3 and PtH (SnCI3)2,(PPh3)2 the first one
known as Wilkinson's catalyst continues to occupy a position of predominant
importance.

The mechanism of homogeneously catalyzed hydrogenations is rather


complicated and has been the subject of much speculation and controversy, but
the accumulated evidence reveals that metal-hydrogen bond (either present in
the parent transition metal complex itself or formed during the catalytic
process) appears to be an essential step in the catalytic cycle, followed by the
coordination and insertion of the alkenes and reductive elimination, the full
cycle is illustrated in Figure 7.1.

For example, the chemistry of hydrogenation involving RhCI (PPh3)3


catalyst can be understood in terms of the following steps (numbered according
to their sequence in the cycle illustrated in Fig. 7.1; triphenylphosphine PPh3 is
for convenience symbolized by (P').

(the above indicates cis hydrogen addition and the same has been established by
'H and 31P n.m.r. spectroscopy; the coordination number of rhodium increases
from 4 to 6 and its oxidation state from +1 to + 3 and hence, the process is
known as 'oxidative addition' of hydrogen).

267
In addition to activation of hydrogen by a oxidative addition process
occurring with Wilkinson's catalyst, alternative routes, e.g. homolytic splitting
and heterolytic fission, have also been suggested for hydrogen activation; these
can be illustrated with the catalysts such as [Co(CN)5]3- (d7) and [RuCI6]3- (d5)
respectively.
hemolytic
3-
2[Co" (CN)5] + H2 2[Co'"H (CN)5]3-
splitting

heterolytic
3-
[RuCI6] +H2 fission [RuHCI5]3- +H+ +CI-

This type of 'heterolytic' activation of hydrogen is more likely with metal


complexes in higher oxidation states, which makes the oxidative addition path
less feasible :

268
In view of the catalyst being regenerated after a cycle of reactions, it
should be possible to represent a catalytic process by a closed loop
incorporating various steps of reactions involved. For example, the above
reactions can be combined in a loop form as represented in Fig. 7.1.

In addition to the hydrogenation reaction by RhCI(PPh 3)3, the


hydridocarbonyltris (triphenylphosphine) rhodium (I) is another effective
hydrogenation catalyst for alkenes.
RhH(CO)(PPh )
H2C =CH2+H2 3
3 CH3-CH3

The chemistry of hydrogenation of an alkene with this catalyst can be


understood in terms of the following sequence of processes (which could be
combined into a cycle as above):

(In spite of the higher stability of the 18-electron systems in general, the
tendency of the above dissociation can be understood on the basis of steric
relief brought about by the dissociation of a bulky triphenylphosphine, PPh3
ligand):

269
(Coordination of alkene to the metal atom polarizes the C-C bond and
allows facile migration of the alkyl with its bonding electron pair):

The unique features of above catalytic steps are (i) hydrogenation of alkenes by
RhH(CO)(PPh3)3 is unusual in its being highly selective for the hydrogenation
of alk-I-ene compared to alk-2ene; and (ii) hydrogenation follows anti-
Marknownikov rule.

The hydrogenation of alkenes has been extended to the synthesis of some


asymmetric products and also to synthesis involving polymer supported
catalysis.

7.4.2. Polymerisation of Alkene (Zieglar Natta Polymerisation)

The polymerization of alkenes to give commercially useful fibres, resign, and

270
plastics is a thermodynamically favoured process. However, the alkene must
first be activated by a catalyst, so that the polymeriazation reaction may proceed
at a reasonable rate. A variety of organometallic compounds have been
frequently used for this activation or catalytic process and the reactions in their
presented generally lead to stereoregular polymers. Stereoregular
polymerization leads to the arrangement of the repeating units in a stereoregular
arrangement and it may be interesting to point out that nature has been
accomplishing the same in an efficient manner all the time. Quartz; the
polysaccharides; starch and cellulose; and the polynucleotides: DNA
(deoxyribonucleic acid) and RNA (ribonucleic acid) are all the examples of
such natural stereoregular polymers.

Before describing the Ziegler-Natta process for polymerization of


alkenes, it would be appropriate to point out that unsymmetrical alkenes can
lead to different types of arrangements in the polymer. Catalysed
polymerization of ethylene (ethene) produces a stereoregular polyethylene
(polythene)

Proplyene, on the other hand, may form two stereoregular (either


isototactic or syndiotacitc) or a non-regular atactic povmer (Figure 7.2.)

(a) Isotactic polymer (In this all methyl groups lie on the same side of the
chain, which teds to adopt a helical shape so that the methyl groups do
not sterically interfere with one another)

271
(b) Syndiotactic polymer (In this, there is a regular alternation of methyl
groups along the chain)

(c) Atactic polymer (In this, there is no regularity in the configuration of


methyl groups along the chain)

Fig. 7.2. Possible configurations (a,b and c) of polypropylene.

Ziegler-Natta polymerization of alkenes.

high tempeature
nC2 H 4     C2 H 4 n
and pressure

The origional uncatalyzed industrial process for polythene involved the use of
high temperatures and pressures and the product was atactic, amorphous, and of
low density. However, K.Ziegler (Germany) and G. Natta (Italy) achieved low
pressure and room temperature stereoregular catalytic polymerization of
ethane and propane in the presence of organometallic mixed catalysts (1955)
to give isotactic, high density, harder and tougher, higher melting crystalline

272
polyethylene ("Polythene") and other plastics on an industrial. scale, for which
they shared Nobel Prize for Chemistry in 1963. A typical Ziegler-Natta
catalyst can be made by mixing TiCl4 and Al2Et6 in heptane. In Ziegler-Natta
type of catalytic system consists of a reducing and/or alkylating agent from
Group I-III such as an aluminium alkyl (usually Al2Et6 or AlClEt2)2, and a
transition metal compound (usually a halide of early transition metal series, e.g.
TiCl4, TiCl3, or VCl4) In fact, Ziegler cites the following rule: take any
organometallic combine it with a compound of a transition metal, and you will
have a good chance of finding a suitable catalyst for your special
polymerization problem"

Most Z1egler Natta catalytic systems are heterogeneous, although several


homogenoeous catalytic procedures have also been developed (e.g. from
TiCl2(n5-C5H5) or TiClEt(n5-C5H5)2 Recetnt studies appear to show that the
polymerization site is generally the transition metal in an activated form, which
is brought about by its reaction with aluminium alkyl (an initiator acting as
reducing and alkylating agent). Although the mechanism of the process is not
completely understood, yet for many years the accepted view for the
functioning of a Ziegler Natta catalyst has been that due to Cossee (1977). The
initiating step, according to Cossee, consists in the replacement of one of the
chloride ions coordinated to a titanium(III) ion {which has been initially
generated in situ from the parent titanium (IV) chloride by reduction with Al 2,
(CH2CH3)6, at the surface by an alkyl "Group of the aluminum alkyl

273
(Fig 7.3.).

Due to the formation of an empty coordination site exposed at the surface of the
alkylated titanium (III) halide, a molecule of propylene (propene) can bind itself
to it through it -electrons (step 2) :

274
This reaction brings the alkyl group and the alkene in proper stereochemical
arrangement to facilitate migration of the alkyl group to alkene (i.e., cis-
insertion in the neighboring metal-alkyl bond), giving a longer chain (i.e.,
growing polymer chain) of the alkyl derivative; this results in a fresh vacant site
at the surface (step 3) :
This vacant site can be occupied by another propene molecule and the insertion
process is repeated and steps (2) and (3) continued until a chain termination
process occurs by the severing of the titanium-alkyl bond :

The vacant site can be occupied by another propene molecule and the insertion
process is repeated and steps (2) and (3) continued until a chin termination
process occurs y the serving of titanium-alkyl bond:

275
Alternatively, the process may be sometimes interrupted by -elimination of a
metal hydride or by hyrolysis :

The stereoregularity or polypropylene was assumed to arise due to the


nature of sterically controlled directing sites on the TiCl 3 lattice.

In marked contract an alternative mechanism for alkene polymerization


which is gaining ground, involves the generation of alkylidene intermediates by
-(or 1,2-) hydrogen transfers. This mechanism which shows close connection
between alkene polymerization and alkene metathesis, provides an explanation
for the control of stereochemistry of the polymerization of propene since
substituents could lie either as cis or trans with respect to the
metallocyclobutane ring. A scheme for propylene polyerization which involves
the following key steps : (i) carbon-carbon bond formation by alkyl migration
(Cossee), (ii) 1,2-hydrgen shift forming an alkylidene hydride, (iii) carbon-
carbon bond forming step by metallocycle formation, and (iv) reductive
elimination.

In this alternative mechanism, the specific nature of stereoregular


polypropylene would be obviously controlled by the relative orientations of the
substituents on the metallocyclic ring. Thus a syndiotactic form of the
polypropylene would be obtained if the CH3 group are on the same side of the
metallocyclic ring.

276
Besides the above two, another view of the possible mechanism which is
currently emerging is based on C-HTi interactions (for which Green and Co-
workers have proposed the term "agostic", to illustrate especially those
situations in which hydrogen atom is covalently bonded simultaneously to both
a sp1 carbon atom and to a transition metal atom).

The Cossee mechanism on the one hand and the hydrogen


migration/metal-carbene mechanism on the other, hand can be seen as extreme
representations of an alkene insertion reaction involving agostic -hydrogen
interactions. The salient features of the above mechanism are : (i) carbon-
carbon bond forming step assisted by the partial migration of an –hydrogen to
the metal giving a C-HHi bond; (ii) the metallocycle intermediate with a -
CHTi bond; (iii) rearrangement of the agostic hydrogen from the - to the -
position; and (iv) addition of the next alkene. In the above figure, the encircled
'P' represents and growing polymer chain. The mechanism based on agostic
hydrogen interactions can explain stereoregular polymerization of alkenes on
the grounds that (i) the formation of an -bridging hydrogen by the alkyl group
would reduce the steric inhibition to the C-C bond forming step, and (ii) the
H

bidentate nature of the Ti  C  H interation coudl provide a means for
H 
controlling the stereochemistry (orientation) of alkyl chain with respect to the
incoming alkene.

It may be worthwhile to mention that an interaction of the type chain


with respect to the incoming alkene.

It may be worthwhile to mention that an interaction of the type

277
H

Cl 2 Ti  C  has been actually observed in the X-ray structure

H  H
recorded recently (1982) of TiCl3CH3 (dmpe).

7.4.3. Hydroformylation of Alkenes ('Oxo' Process)

The reactions involved in the process are in principle the addition of


hydrogen (-H) and the formyl (-CHO) group to alkenes leading to the formation
of aldehydes, which are generally precursors for the production of higher
alcohols (usually C6-C9):

Earlier, the reactions used to be catalyzed by cobalt carbonyl CO 2(CO)8,


which was not so effective a catalyst as the reaction had to be carried out at
high (150-1800C) temperature and pressure (200 atmospheres). Further the
products were generally mixtures of linear and branched-chain isomers in
roughly 3 : I ratio ; the formation of these is directed by anti-Markovnikov and
Markovnikov additions respectively, e.g.:

The role of the cobalt catalyst, CO2(CO)8 can be illustrated by a catalytic cycle
shown in Figure 7.4 :

278
Fig. 7.4. Catalytic Cycle for hydroformylation of alkenes by cobalt catalyst.

The cobalt process thus suffers from a number of disadvantages such as :

(a) volatile nature of CoH(CO)4 leading to its loss along with the product
aldehyde and requiring its separation which is generally done in the
form CoSO4.

(b) loss (-15%) of the alkene by a side hydrogenation reaction,

(c) a small amount of the conversion of aldehydes into alcohols by


hydrogenation.

(d) production of generally less useful branched chain aldehydes and

(e) drastic conditions (high temperature and pressure).

279
A comparative perusal of these hydroformylation and hydrogenation
reactions shows their mechanistic similarity. A number of catalysts like
RhH(CO)(PPh3)3 can, therefore, be effective in both types of reactions.

More recently it has been found that the platinum group complexes such
as RhCl(CO)(PPh3)3, RhH(CO) (PPh3)3 and Ru(CO)3(PPh3)2 are much more
effective than cobalt complexes. These new complexes facilitate the reactions
much more effectively to proceed at lower temperatures and pressures.

For example, with RhH(CO)(PPh3)3 as catalyst, the hydroformylation


reactions can proceed under ambient conditions (250C and atomspheric
pressure) o yield aldehydes almost quantitatively.

In addition to more moderate working conditions, another distinct


advantage or the rhodium catalyzed reactions is their high selectively for the
formation of only the straight chain aldehydes particularly in the pressure of
excess phosphine (PPh3). This excess phosphine tends to suppress effectively
the lower dissociative tendency of the intermediate rhodium bis-complex,
RhH(CO)(PPh3)2, thus favouring the associate attack of the alkene on the above
bisphosphine complex (Fig. 7.5) for which the specificity of the anti-
Markownikoff addition is higher. For example, the hydroformylation of
propene in the presence of Co2(CO)8 yields a mixture of normal and
isobutyraldehyde. The ratio of normal to iso-isomers is increased with the
rhodium catalyst and in presence of excess phosphine mainly the normal
butyraldehyde is obtained.

In spite of the efficacy of the rhodium catalyst under ambient conditions,


higher temperature (-1000) and pressure (a few atmosperes) are actually
employed in the Union Carbide process. In this connection, it may be

280
emphasized that the conditions for any reaction at the industrial scale are
chosen in a manner so that the process has an optimum economic feasibility.

The mechanism consists of the following sequence of processes :

(1) Lewis base (PPh3) dissociation; (2) Alkene coordination;

(3) Ligand combination; (4) Lewis base (CO) association;

(5) Ligand combination; (6) Oxidative addition

(7) Reductive elimination;

(8) Lewis base (PPh3) association and catalyst regeneration.

For substantiation of the suggested reaction mechanisms, attempts are generally


made to isolate the presumed intermediate products. The rhodium intermediates
of the catalytic cycle shown in Figure 7.5 appear to be too labile for isolation.
However, with tetrafluoroethlylene (C2F4), square planar stable complexes such
as Rh(C2F4H) (CO)(PPh3)2 have been isolated. Indirect evidence for the other
rhodium intermediates (except dihydridoacyl complex) is based on the
characterization of more stable iridium analogues. Although it has not been
possible to actually isolate even iridium analogue of the dihydridoacyl complex,
a similar derivative, IrHCl(COCH2R) (CO) (PPh3)2 has been characterized.

281
Fig.7.5 Catalytic cycle for the hydroformylation of alkence
(p*represents PPh3)

In addition to the above mentioned catalysts, a ruthenium complex


Ru(CO)3 (PPH3)2 has also been found effective. Although the basic catalytic
steps are similar to those described in Figure yet the mechanism of
hydroformylation reaction is of a different pattern.

7.4.4 Oxidation of Alkere (Oxo Palladation), Wacker Process:

One of the first processses to highlight the importance of alkenes in the


production of a wide variety of organic compounds was the Wacker process
developed in Germany in the early 1960's this is an important large scale
industrial process for the production of acetaldehyde, acetone, and methlyl ethyl

282
ketone. It has been stated that "the invention of the Wacker process was a triuph
of common sense". It may be noted that the oxidation of ethylene to
acetaldehyde with the help of platinum group metals had been known as for
back as 1894:

heat
[PtCl3(C2H2)] + H2O   CH3CHO + Pt (O) + 3Cl
-

Zeise's salt

It was, however, more than six decades later that Smidt working at
Wacker Chemie laboratories discovered a practical process for the oxidation of
ethylene to acetaldehyde using PdCl2 as a catalyst. For the mechanism of the
reaction, the following sequence of key-steps has been proposed on the basis of
extensive kinetic and other investigations:

(a) Alkene coordination to a metal complex,

[PdCl4(C2H4)}- +H2O[PdCl2 (H2O) (C2H4)]+Cl-

(b) Nucleophilic replacement of another Cl by H2O

[PdCl4]2 + C2H4  [PdCl3(C2H4)]+Cl

(c) Intermolecular attack of H2O on the coordinated ethene, followed by loss of


H to form hydroxometal complex.

[PdCl2(H2O)(C2H4)] [PdCl2(H2O)](C2H4OH)]-+H+

(d) β-Hydrogen elimination and (e) Migratory insertion into Pd-H bond.

283
(e) β-Hydrogen elimination

(f) Finally, acetaldehyde is produced in another β-elimination. followed by a


base dissociation reaction

284
Fig. 7.6 : Wacker Process Catalytic Cycle

(g) Catalyst regeneration .


Although formation of the species, [PdCl3( (C2H4)]2 (an analogue of
Zeise's salt) has been postulated in the first step (a) of the above mechanism, it
may be pointed out that this derivative has not so far been isolated (In fact, the
dimeric complex [PdCl3( (C2H4)]2 has been isolated by the reaction of the
components in non-aqueous solvents).

The role of copper (II) chloride in the Wacker process (Fig 7.6) appears
to be the regeneration of the catalyst [PdCl4]2 species by oxidation of Pd(O),
getting itself reduced to Cu(I) state which is oxidized by oxygen in the presence
of HCl back to the +2 oxidation state:

(i) Product (acetaldehyde) formation.


[PdCl4]2- + C2H4 + H2O CH3 CHO + Pd(O) + 2HCl +2Cl

285
(ii) Catalyst, [PdCl4]2- regeneration,

Pd(O) + 2CuCl2 +2Cl [PdCl4]2- + 2CuCl

(iii) Co-catalyst (CuCl2) regeneration,

2CuCl + 2HCl + I/2O2 – 2CuCl2 + H2O

The overall reaction can, therefore, be represented as


C2H4 + I/2O2 CH3CHO

Steps (a) to (f) in the suggested mechanism of the Wacker process can be
represented by a cycle (Fig. 7.6) in which the reactants entering and the
products leaving the system are indicated at appropriate place. By inclusion of
the reactions representing the catalyst and co-catalyst generation the cycle is
completed.

7.4.5 Synthetic Gasoline


Synthesis of gasoline from synthesis gas is an old process, which use
heterogeneous catalyst :

NCO + (2n+1) H2 catalyst Cn H2n+ 2 + nH2O 

Synthesis gas (H2/CO) may be prepared from coal. This is an important


starting material for many industrial chemicals (aldehydes, alcohols, acids and
gasoline)

For the first time (H2/CO) mixture was prepared in the form of water-gas
by passing steam over red-hot coke. The ratio of hydrogen and carbon
monoxide can be changed using water gas shift reaction, in which reactants are
catalyzed using many homogeneous and heterogeneous catalysts.

286
C + H2O CO+H2
Hot + Steam Water gas

CO + H2O  CO2 + H2

Now a days use of homogeneous catalyst has become very common, and
metal carbonyl complexex, such as {HFe (CO)4}, {Rh(CO)2I2}and {Ru (bpy)2
(CO) Cl}+ have been found very useful homogeneous catalyst for this reaction.

The scheme of the reaction catalysed using {Ru (bpy)2 (CO) CL}as a
homogeneous catalyst is shown in fig 7.7.

Fig. 7.7

Now a days synthesis gas is produced from methane;


CH4 + H2O  CO + 3H2

We know, synthesis gas obtained from natural gas (CH4) can be

287
converted into methanol:

CH4 (H O)
2 H2 + CO  CH3OH

Mobil (1988) in Newzeland, developed a method to convert methanol


into gasoline using zeolite (ZSM-5) catalyst. Although the exact mechanism is
not known, but the complete reaction may be written as follows :

nCH3OH ZSM-5 – (CH2)-n + n H2O

The most important characteristic of zeolite catalyst, ZSM – 5, is that the


size of its pores is quite suitable for gasoline molecules. The insertion of
methylene in the molecule continues untill the size of the molecule equals the
size of pores. At this state (C8 to C10 Chain formation) insertion – reaction
automatically stops.

Fischer – Tropse reaction is an old process for manufacture of gasoline.


This process uses a heterogeneous catalyst. This process may be regarded as
reductive polymerisation of carbon monoxide, in which molecular hydrogen
functions as a reducing agent,, carbon chain increases by carbene insertion.
Now a days, in this reaction, dirhodium complex is used as a homogeneous
catalyst. The propagation step in Fischer- Tropse reaction may be understood to
take place as follows :

288
The bridged carbene of the dimetallic complex, which is analogous to
surface carbene of the heterogeneous catalyst (Fischer – Tropse Process), takes
part in formation of C-C bond.

CHECK YOUR PROGRESS – 2

Notes : (i) write your answers in the space given below :

(ii) Compare your answers with those given at the end of the unit.

(a) (i) The homogeneous catalyst used in hydrogenation of alkene is


............................ It is used in the production of industrially important
compounds such as .........................and .....................................................

(ii) During hydrogenation, this homogeneous catalyst


................................................. and is converted in to a very reactive
........................ which by .............................................................of
.................................loses one ligand and is converted into a saturated
complex combining with........... In the last step......................is obtained
and the catalyst molecule is regenerated.

(iii) The homogeneous catalyst........................, used inpolymerisation of


alkene is ........ .................... or ................................... . This catalyses
polymerisation of alkene by ....................................... steps. The insertion
takes place at ........................... before ............................ .

(b) (i) Oxo-reaction is the ................................reaction. The two important


organometallic catalyst used in this reaction are
.......................................... and .................. out of these .............................
is proved very effective.

289
(ii) Oxidation of alkene is known as ............................. or ............................
process. In this process ..................................... along with
......................... is used as a catalyst.

(iii) The main steps in this process are.

1. _______________________

2. _______________________

3. _______________________

4. _______________________

5. _______________________

6. _______________________

(iv) Now a days gasoline is synthesised using .............................. catalyst.


The most important ruthenium catalyst amongst these has molecular
formula ........................

Using Zeolite catalyst, .........................., ....................... is converted into


................ The complete reaction is :

7.5 LET US SUM UP

After going through this unit you would have achieved the objectives stated at
the start of this unit. Let us recall what we have discussed in the unit:

 Many organotransition metal compounds have been used as


homogeneous catalyst in the manufacture of industrially important
compounds. The various important processes which take part in the

290
catalytic mechanish are as follows:

(i) Oxidative addition,

(ii) Insertion and elimination and

(iii) Nucleophitic addition of coordinated ligands.

 Oxidative addition is the first step in a catalytic process, in which


bonding between transition metal and the reactants takes place. A very
important example of this process is Vaska Complex, (Ir (CO)L 2 Cl)
(where, L=PPh3). These reactions have been proved quite important in
the synthesis of many new and novel compounds.

 For oxidative additions, it is necessary that the metal ion must possess
vacant coordination place and also should have suitable orbital for
bonding.

 The mechanism of oxidative addition depends on nature of reactant, xy.


If xy is nonpolar (eg.H2), then a tricentred intermediate product is formed
in the reaction. If xy is electrophilic and polar (eg. CH3I), then oxidative
addition follows SN2 reaction.

 For oxidative addition, in addition to the availability of coordination


positions, important factors are :

(i) Ease of oxidation,

(ii) Relative stability of coordination number, and

(iii) Higher strength of the newly formed bond (M-X), compared to that
of the breaking bond (X-Y)

291
 In cases of agostic association (behaviour of C-H as ligand), oxidative
addition takes place through intermolecular cyclometallation or
orthometallation process.

 Insertion reactions are those reactions, in which oxidation states of metal


ion is not changed. The inserted molecule is added in between metal-
carbon or metal-hydrogen bond. The reverse of this reaction is
decarboxylation or elimination reaction.

 An important example of elimination reaction is β-hydrogen elimination.


Other important processes are:

(i) Reductive elimination

(ii) Radical formation

(iii) Alkene/arene displacement

(iv) Transfer of electron from metal to reductant, and

(v) Carbanoid ligand elimination.

 Coordinated unsaturated hydrocarbons are specially fond of


nucleophilic addition: although they do not take part in these
reactions, but in the coordinated state due to transfer of electron
density towards metal atom, they develop affinity for these reactions.

 In industrial important reactions organotransition metal complexes


have proved better homogenous catalyst.

 Many transition metal ions, viz Ru(III), Ru(II) Co(II), Co(I), Rh(I),

292
Ir(I) , Pd(II), Pt(II), Ag(II), Ag(I) and Cu(I) reduce activation energy
of hydrogenation reaction and catalyse it.

 For hydrogenation of alkene, the most important homogeneous


calalyst known is wilkinson catalyst, it is used in the production of
margarin, pharmaceuticals and petrochemicals.

 The first step in homogeneously by catalysed hydrogenation reaction


is oxidative addition of hydrogen in the catalyst, resulting in
formation of hydrido complex.

In second step, this hydrido complex, losing one phosphine ligand,


gives an unsaturated complex.

The unsaturated complex in the third step coordinates alkene molecule


to give a saturated complex.

In fourth step, this results in an intermediate product after β-hydrogen


insertion.

The intermediate product in fifth step takes on phosphine ligand to


form saturated compound.

In the last sixth step, as a result of reductive elimination reaction,


hydrogen is transferred on carbon atom: resulting in formation of an
alkane, with regeneration of the catalyst.

 In polymerisation reaction of alkenes, Ziegler-Natta is used as an


important homogeneous catalyst, eg.Ti Cl2 (η5-C5H5)2.

 One Ziegler-Natta cyclic complex, ¿ (η5-C5H5)2 Zr (CH3) (thf),

293
catalyses polymerisation of alkene in continuous insertion steps. The
insertion takes place before the coordination on electrophilic center-
Zr.

 Hydroformylation of alkene is known as oxo- reaction. This reaction


converts alkene into an aldehyde.The catalyst is either cobalt or
rhodium carbonyl complex.

 According to the proposed mechanism:

In step I - Reaction of hydrogen with the catalyst, Co2


(CO)8, results in formation of CoH (CO)4

In step-II - This loses one CO molecule to give an


unsaturated complex, CoH(CO)3A

In step III - It a coordinates to give saturated complex.

In step IV - Insertion of alkene in Co-H bond results in an


unsaturated complex.

In step V - Coordination with CO results in formation of


RCH2CH2 Co(CO)4 complex.

In the last, step VI- Mobile insertion releases an aldehyde and the
catatlyst is regenerated.

 Now a days, rhodium catalyst RhCl (CO) (PPh3)3 is prefered in place


of cobalt catalyst. Other important effective catalyst is ruthenium
catalyst, Ru (CO)3 (PPh3)2.

 The main step in the catalystic reaction of rhodium catalyst are:

294
1. Elimination of Lewis base, PPh3

2. Combination with alkene

3. Ligand association

4. Combination with Lewis-base, CO.

5. Ligand Association

6. Oxidative addition

7. Reductive elimination

8. Combination with Lewis base and regeneration of the catalyst.

 Oxidation of alkene is known as Oxo-Palladation or wacker-process,


This reaction is used to prepare many industrially important
compounds, such as acetadehyde, acctone, ethyl (methyl) ketone etc.
The catalyst used in this reaction is PdCl2 along with CuCl2.

The main steps in the catalysed reaction are:

1. Association of alkene in palladium complex and elimination of Cl

2. Nucleophilic displacement of other Cl-

3. Formation of hydroxo-metal complex.

4. β-Hydrogen elimination

5. Mobile insertion in Pd-H bond.

6. β-hydrogen elimination resulting in production of acetaldehyde.

295
 Synthetic gasoline is being prepared from synthesis gas (H 2+CO)
using heterogeneous catalyst.

Now a days it is synthesised by using homogeneous catalysts such as


{H Fe (CO)4,}, Rh(CO)2 I2 , Ru(bpy)2 COCl etc: which have been
proved effective catalysts.

 Mobil used zeolite catalyst, ZSM-5 to convert methonol into gasoline:

η(CH2OH) zsm-5 - (CH2)η- + ηH2O

7.6 CHECK YOUR PROGRESS : THE KEY

1.(a) (i) (x) Oxidative addition

(y) Insertion and elimination

(z) Nucleophilic addition on coordinated ligands.

(ii) elimination

primary step

bonding

reactants

(iv) coordination positions

metal ion

suitable orbital

(b) (i) oxidation state

296
metal ion

metal – Carbon or metal – hydrogen bond

(ii)(x) β-hydrogen elimination

(y) Reductive elimination

(z) Carbanoid ligand elimination

(iii) unsaturated hydrocarbons

receptive

do not

transfer of electron density towards metal

receptive

2(a) (i) Wilkinson catalyst.

margarin, pharmaceuticals

petrochemicals

(ii) loses one phosphine Ligand

tricoordinated Complex

oxidative addition

one molecule of hydrogen

the alkene

297
alkane

(iii) ziegler – Natta

TiCl2 (n5 – C5 H5)2

TiCl (C5H5) (n5 – C5 H5)2


continous insertion

electrophilic – Zr

coordination.

(b) (i) hydroformylation of alkene

CoH (CO)4

HRh (Co) (PPh3)3

HRh (Co) (PPh3)3

(ii) oxopalladation

Wacker Process

PdCl2

CuCl2

(iii) 1. Coordination of alkene in Pd – complex and elimination Cl-

2. Displacement of other Cl- by water molecule.

3. Formation of hydroso-metal complex.

4.  - hydrogen elimination

298
5. Mobile insertion in Pd-H bond

6. Production of acetal dehyde by  - elimination.

(iv) homogenous

[Ru (bpy)2 (Co) Cl]

ZSM – 5

methanol

gasoline

n CH3OH ZMS – 5 - (CH2) n - + n H2O.

299
UNIT – 8 FLUXIONAL ORGANOMETALLIC COMPOUNDS

Structure

8.1. Introduction

8.2. Objectives

8.3. Fluxional Behaviour

8.3.1. Methods of Study

8.4. Fluxional Behaviour of 2 –Olefin Complexes

8.4.1. Fluxional Behaviour of Alene Complexes

8.4.2. Fluxional Behaviour of -bonded Cyclic Alkenes

8.5. Fluxional Behaviour of 3 – Allyl – Complexes

8.6. Fluxional Behaviour of Dienyl Complexes

8.7. Let Us Sum Up

8.8. Check Your Progress : The Key

300
8.1. INTRODUCTION

No molecule is strictly regid even at 0 K due to the interatomic vibrations, but the amplitude
of vibration about mean position is about 10-30 pm. However, some molecules, like PFs,
some metal carbonyls and organometallics, called fluxional molecules, undergo
deformational rearrangements in which the atoms actually interchange their places with one
another. In case of PF5, for example, rapid exchange of the axial and the equatorial fluorine
atoms in the trigonal pyramid structure through the intermediate square pyramid (>105 5-1)
makes the NMR spectrophotometer record all the fluorine atoms in an identical environment
which is the weighted average of that prevailing in the separate environments (Fig. 8.1.).

Because of the small difference in the energies, the 5-coordinate (TBP→SP→TBP) and the
8-coordinate complexes (square antiprism→ dodecahedron→square antiprism) are generally
fluoxinal even at low temperature.

In this unit we shall analyse different transition metal organometallic compounds for
fluxional behaviour.

8.2. OBJECTIVES

The main aim of this unit is to analyse different transition metal organometallic
compounds for their fluxional behaviour. After going through this unit you should be able to:

 describe what is fluxional behaviour and fluxionality,


 discuss the factors on which fluoxinal behaviour depends,
 describe the various methods used to study fluxional behaviour of compounds, and
 explain fluxional behaviour shown by different transition metal organometallic
compounds, eg. olefins, alenes, cyclicalkenes, allyls and dienyl complexes.

8.3. FLUXIONAL BEHAVIOUR

The structures of a number of organometallic compounds have been described. In


most of the cases, these structures are unique and well-defined. The atoms of the molecule

301
are ofcourse continuously involved in approximately harmonic vibration about their
equilibrium positions, but in other respects the structures may be considered rigid.

As stated in the last-chapter also, alkene complexes of transition metals represent a


special class of compounds, in which the molecular vibrations or intramolecular
rearrangements change a molecule from one type of configuration into another. Such
molecules have, therefore, more than one thermally accessible structures, which under
suitable conditions (especially of temperature) are interconvertible from one to another fairly
rapidly. This phenomenon may be termed as 'fluxional behaviour'.

In other words, if the two or more configurations are equivalent (in structure, bonding
and energy content). Such molecules are called fluxional (name suggested by Doering and
Roth, 1963).

An alternative term 'Stereochemical nonrigidity' has been suggested (by Muetterties,


1965) for the latter type of 'fluxional molecules'. However, F.A. Cotton, a prominent worker
in this field, has suggested (1968) that the term 'stereochemical non-rigidity' be reserved as a
general term for molecules of both the above types, i.e., tautomeric and fluxional, which
undergo rapid reversible intramolecular rearrangements.

The development of the concept of 'fluxionality' in molecules has an interesting


history. In view of the novelty of the idea and involvement of prominent organometallic
chemists, the historical development of the concept is being presented in a little more detail
and examples of even some simple inorganic molecules like PF5 have been included for
elucidating the concept before presenting the features of a few 'fluxional' organometallic
compounds. Although the n.m.r. non-equivalence of the fluxional atoms in PF5 was reported
by Gutosvsky and coworkers in 1953, yet a fuller understanding of the accompanying
phenomenon had to wait till the commercial n.m.r. spectrometers became available in late
fifties.

In systems such as PF5 and Fe (CO)5 fluxional behaviour was first detected. In 19and
13
C n.m.r. spectra respectively of the above two molecules, only one resonance peak was
observed instead of two in the ratio of 3:2 (i.e. ratio of axial to equatorial sites).

302
From theoretical considerations, it can be concluded that when two nuclei, the
resonance frequencies, of which differ by (v1-v2)= v/sec., change site at a frequency higher
than (v1+v2)/sec., then only one resonance peak would be observed at the mean (v1+v2)/2
position of the two frequencies characteristic of two types of sites, between which
interchange is occuring.

In both PF5 and Fe (CO)5 the dissociative or bimolecular mechanism appears to be


ruled out in view of the persistence of 35P-19F and 57Fe-13C coupling. although the probability
of 1-for-1 exchange in which one equatorial and one axial ligands are involved in each step
cannot be ruled out, the available experimental evidence appears to favour a 2- for-2 process
in which axial ligands exchange simultaneously with two equatorial ones. The most probable
mechanism for this type of exchange was suggested by Berry in 1960 as follows (fig. 8.1).

Fig. 8.1(a) Berry Psuedorotation

8.1(b) TBP and SP conformation minima

The exchange process involves change from tbp model to sp intermediate by


simultaneous closing of the F1PF2 angle from 180º and opening of the F4PF5 angle from 120º
so that both attain the midway value, giving rise to the square set of atoms F1, F2 F4, F5 all

303
equivalent to one another. The sp configuration (b) could return to the original tbp
configuration (a), or go a step further to attain the new tbp configuration (c) in which the
molecules have effectively rotated round the F3P axis through 90º. In view of this apparent
rotation. Berry mechanism is termed 'pseudorotation.

The first unambiguous evidence for a rapid intramolecular rearrangement in a d8


pentacoordinate transition metal complex was reported by Udovich and Clark in 1969. the
19
variable low-temperature F n.m.r. spectrum of the compound (Fig. 8.2), Similarly (CH3)
PF4 also shows this type of behaviour.

Fig. 8.2(a) 19F NMR Spectra at-22ºC

Fig. 8.2 (b) 19F-NMR spectra at -143º

The first observations leading to the concept of fluxional behaviour of organometallic


molecules appear to have been made in 1956 by Pipe and Wilkinson, when they observed in
the respective proton n.m.r. spectra, only a singlet for Hg(1-C3H5)2; two singlets for the two
cyclopentadienyl ligands at the room temperature in Fe(1-C3H5)(CO)2(5-C3H5) and a
singlet for all five ring protons in Cu(1-C3H5)P(C2H3)3:

The next observation relevant to this field was the observation of a single 13C peak in
the n.m.r. spectrum of Fe(CO)5, which according to the two plausible structures, trigonal

304
bipyramid (tbp) and square pyramid (sp), was expected to give two signals in the ratios of 2/3
or ¼ respectively. The observation about the appearance of only a single peak was confirmed
by Nyholm and coworkers (1962) who believed in the 'sp' structure contrary to the 'tbp'
structure assumed by Cotton and coworkers. Incidentally, the structure in the solid state has
been established (1974) by X-ray crystallography to be of the 'tbp' type.

8.1.1 Methods of Study

Out of the different spectroscopic tools (microwave, infrared, and nuclear magnetic
resonance spectroscopy), the n.m.r. technique has proved to be of maximum utility in the
study of fluxional behaviour. For a number of systems, the speed of rearrangement is fast
enough at the ambient temperatures for the n.m.r. techniques not be able to detect the same,
but at lower temperatures the rearrangements become slow enough to be detected by n.m.r.
spectroscopy (Table 8.1).
Table 8.1
Time scale for selection of the method for study of structures

Method Approximate Time Scale(s)

Electron diffraction 10-20

Neutron diffraction 10-18

X-ray diffraction 10-18

Ultraviolet spectroscopy 10-15

Visible spectroscopy 10-14

IR-Raman spectroscopy 10-13

ESR-spectroscopy 10-4 to 10-8

NMR spectroscopy 10-1 to 10-9

The choice of a technique suitable for the study of a fluxional system would

305
obviously depend on the rate of rearrangements in a specific case. From this point of view,
the spectroscopic techniques could be divided into two broad groups.

(a) In some fast techniques like electronic and vibrational spectroscopy and gas phase
electron diffraction, the act of observing the molecule is completed in <10-11 sec.
Process of rearrangement are generally not fast enough to influence these
observations. Thus by these techniques, (i) no fluxional behaviour would be expected
to be observed if the different configurations are equivalent and (ii) for tautomeric or
isomeric molecules, both forms will register their presence in the spectrum, but no
indication of the inter conversations could be possible.

(b) The rearrangements involved in stereochemically non-rigid behaviour are rate


processes with activation energies of different magnitudes. When these activation
energies are in the range of 25-100 kJ mol-1, the rate of rearrangements can be
brought generally between temperatures of +150-to-150ºC into a range in which the
signals due to different fluxional species can be detected separately by n.m.r.
technique. Thus by proper choice of temperature, many such rearrangements can be
controlled so that they are slow enough at lower temperatures to allow signals due to
different fluxional species appearing distinctly, and rapid enough at higher
temperatures for the signals from the different configurations or environments to be
averaged into a single line at a mean position.

Normally, studies of fluxional molecules are carried out with the following two main
objectives:

(i) establishing definitely the instantaneous structure (for which information can
be achieved by recognising the limiting spectrum) of the molecule; and

(ii) to study the pathway of rearrangement.

These targets can be conveniently achieved by n.m.r. line shape analysis and this
technique will, therefore, be discussed in some detail.

306
8.4. FLUXIONAL BEHAVIOUR OF 2-OLEFIN COMPLEXES

Alkenes are in general rigidly bonded to the transition metals and these complexes
are, therefore, often fluxional in nature. As discussed nmr (particularly'H) studies provide an
insight into such behaviour of complexes in solution. It has been found that the solid state
structures do not often persist in solution and these studies, therefore, assume special
importance in such cases where complexes are used in solution state in their industrial
applications. Non-rigid attachment of alkenes to transition metals generally permits rotation
either of a barrel-type (i.e. the rotation of metal- alkenes axis).

The above phenomenon of the non-rigid attachment of alkenes to transition metals


has been investigated for the complex, (5-C5H5) Rh (C2H4)2 (Fig.8.3) by the application of
1
H n.m.r. spectroscopy. The spectrum of the complex was found to vary with temperature
(Fig.8.3). The spectrum recorded at-19ºC depicts two distinct types of environments about
the protons. The protons labelled as Ho (outer) appear to give the downfield multiplets (d)
and the upfield multiplets (u) could be ascribed to the inner protons, Hi. These discrete
signals were explained on the basis that at the low temperature, the rotation of the olefin
becomes so slow that it does not affect the observation in the n.m.r. spectrum of the two
distinct environments for the protons in the molecule. However, as the temperature is raised,
the rotation of ethene molecule about the metal-alkene bond tends to make all the ethene
protons magnetically equivalent and the separate lines collapse into a broad signal. An
analysis of the line shape indicates that the activation energy of the rotation process is 63 kJ.

Fig.8.3. H1-nmr spectra of (5-C5H5) Rh (C2H4)2 complex at different temp.

307
In addition to the explanation of the nature of the variable temperature n.m.r.
spectrum observed for the molecule on the basis of rotations another possible interpretation
could be on the basis of intermolecular exchange of ethene molecule. The latter possibility is,
however, ruled out by the high rhodiumethene dissociation bond energy which has been
separately measured as~130kJ mol-1.

A study of the variable temperature n.m.r. study of the molecule, (Fig. 8.3) helps to
distinguish between the two types of rotation. The 1H n.m.r. spectrum of the molecule at-
90ºC does show two sets of resonance lines of equal intensity (one for two ethene protons
closer to CO and the other for the two protons in the proximity of NO), but these coalesce to
a broad signal at-65ºC. However, compared to the simple complex, (5-C5H5) Rh (C2H4)2 this
31
osmium complex (8.4) incorporates two PPh3 ligands also, the P atoms of which begin to
show spin-spin coupling with the four equivalent ethene protons at still higher temperatures
to give a triplet with intensities in 1:2:1 ratio. This coupling between protons and phosphorus
atoms is observed in higher temperature spectrum. This observations lends support to B
13
rather than A type rotation. These conclusions are further corroborated by the C spectrum,
which shows for the ethene ligand at 20ºC only one 13C line, which splits into two equivalent
lines when the temperature is lowered.

Fig. 8.4

8.4.1 Fluxional behaviour of alene complexes

The fluxionality phenomenon is also seen in tetra-alene iron carbonyl. At temperature


below- 60°C its 'H. n.m.r. gives three peaks, which are due to three cisH(s) and three trans.
H(t) and three hydrogen present in the perpendicular plane of six C-Fe bonds (which are
present in different situations). But on increasing the temperature, these three peaks are

308
converted into only one peak, which shows all the hydrogen equivalent. This is probably due
to the transient configuration during mobility of iron atom in alene -system. (Fig. 8.5).

Fig.8.5

8.4.2 Fluxional Behaviour of - Bonded Cyclic-alkenes

A few compounds of cyclic alkenes, in which free alkene ligands has more -
electrons available than the number required to satisfy the 18 Electron or Effective Atomic
Number Rule, are listed below:

Fe(CO)3(4-C8H8); Mo(CO)3(6-C8H8); Cr(CO)3(6-C8H8);

W(CO)3(4-C8H8); Co(4-C8H8)(5-C5H5);Fe2(CO)5(3-C8H8);

Fe(CO)3(5-C7H7);Cr(5-C5H5); (-C7H7);Mo(CO)2(5-C5H5) (-C7H7);

Co(CO)3(5-C7H7);Cu(4-C6Me6); (6-C6H6);Mo(CO)2(5-C5H5) (3-C7H7);

Mn(CO)3(5-C7H7);Mn(CO)2(2-C8H8)(5-C5H5);Fe(CO)2(2-C8H8) (5-C5H5);

Ru(CO)3(4-C8H8);and Nb(5-C5H5)2(2-C7H9).

It has been shown by n.m.r. spectroscopy that in solution these molecules generally
undergo rapid intramolecular rearrangement which is recognized by fewer lines in the
spectrum than one would expect for the static molecule.

The 'H n.m.r. spectrum (Figure 8.6) of Fe(CO)3(4-C8H8) consists of only a singlet
(5.2) at room temperature which splits to give two broad signals (as shown in Fig. 8.6 at-

309
45ºC. The spectrum is of A2H2M2X2 type with two peaks of almost equal intensity indicating
that eight alkenic protons can be divided into two equal groups of four coordinated and
another four uncoordinated ones:

Fig. 8.6. The 'H n.m.r. spectrum of Fe(CO)3(4-C8H8) at-145ºC (60MHz).

There has been considerable controversy regarding the assignments of the two signals
in the above spectrum as well as on the actual instantaneous structure and the rearrangement
pathway.

An instantaneous structure (Figure 8.7) at low temperatures as suggested by Kreiter


and coworkers (1966), may be represented as below:

Fig. 8.7 Suggested structure of Fe(CO)3(4-C8H8)

This structure has been supported by X-ray structural determination confirming that it
is of the (1,3-diene) metal type. Keller and coworkers (1966) have however, argued in favour
of a dynamic exchange (Fig. 8.8)

Fig. 8.8 Dynamic exchange in Fe(CO)3(4-C8H8)

Cotton and coworkers (1966), on the other hand, have suggested a static tub-bonded

310
C8H8 structure (Figure 8.9); in which coordinated alkenic protons give rise to the high field
signal.

Fig. 8.9. Cotton's suggestion for structure Fe(CO)3(4-C8H8)

Cotton's suggestions have received support from a study of the n.m.r. spectrum of
methyl –d-cyclooctatetraene-2,3,4,5,6,7-d6-iron tricarbonyl by Anet and coworkers (1967),
who showed that the terminal and internal protons of the 1,3-diene moiety coordinated to
iron show little difference in chemical shift. In spite of evidence cited above for Cotton's
structure (Fig. 8.9), some more data have been accumulated favouring structure 8.7 also. The
story, therefore, is still incomplete and requires more refined and penetrating measurements
as well as interpretations.

With the intuition that the behaviour of ruthenium complex would be similar to that
of its iron analogue and rate of rearrangement may be slower, Cotton and coworkers (1969)
prepared and studied the complex Ru(CO)3 (4-C8H8). The observed spectra are
demonstrated in Figs. 8.10.

8.10. Variable temperature 'Hn.m.r. spectra of Ru(CO)3(4-C8H8)

311
The spectra of Ru(CO)3(4-C8H8) at the lowest temperatures are essentially limiting
spectra (even spin-spin hyperfine structure may be seen), and demonstrate fully without
anomalies or ambiguities that the instantaneous structure is of the 1,3-diene metal type. The
technique of computer simulation of spectra was employed to ascertain the rearrangement
pathway. Out of various possible pathways (e.g.1,2-;1,3-;1,4- and random shifts), the
computed spectra for the except 1.2 shifts were in gross qualitative disagreement with the
observed specta. For the 1,2-shifts, the agreements is very close, as comparison of Fig. 8.10.
and 8.11 will show.

Similarly, in Os3(CO)10–M-3(3-CH3CH2CCCH2CH3) type organometallic crystals,


due to easy movement of ligands on metal surface, fluxional behaviour is seen (Fig. 8.11.)

Fig. 8.11. (a) NMR at high temperature


(b) NMR at low temperature

8.3. Fluxional Behaviour in 3-Allyl Complexes

A large number of holmoleptic as well as heteroleptic -allyl complexes of both


transition and non-transition metals such as :

Pt ( 3  C3 H 5 )( 5  C5 H 5 ); Co(CO)3 ( 3  C3 H 5 ); Mn(CO) 4 ( 3  C3 H 5 );

Zr( 3  C3 H 5 ) 4 ; Cr ( 3  C3 H 5 ) 3 , Ni( 3  C3 H 5 ) 2 ;

Mo(CO) ( 3  CH 2C6 H 5 )( 3  C3 H 5 ) 2 ; and

312
Zn(3-C3H5)2 are known. In these complexes, the instantaneous structure may be
represented either by localized -bonding (Fig.8.12.a) or delocalized -bonding. (8.12.b)

In the -complex (8.12.a), the two hydrogen atoms on - and -C atoms would be
magnetically equivalent to each other. However, for 3-allyl complexes (8.12.b).

Fig. 8.12.  and  bonded complexes.

which are rigid on the 'Hn.m.r. time-scale, the syn and anti hydrogens
(Hb and Ha) both exhibit a doublet due to the coupling with the central hydrogen (Hc) which
shows a multiplet. Typical n.m.r parameters observed are : He,  6.5-4; Hb, 5-2.5; Ha,  3-1;
J7Hz,  Jac 11 Hz, and Jab  0Hz.

The -allyl group often behave as an electron-rich moiety, but in some of these
reactions there appears to be prior dissociation of one terminus to form an intermediate -
allyl moiety. This kind of system is often reversible and fairly facile, leading to fluxional
rearrangement on the 'Hn.m.r. time scale.

In the -allyl system there is free rotation about the carbon-carbon single bond, so that fascile
groups. 3 to 1 rearrangement provides a mechanism for exchanging the syn an anti groups.
It my be noted that the transformation 3 to 1 ( to ) allyl creates a vacant coordination site
on the metal. The rearrangement of  to  form undoubtedly accounts for the wide range of
reactivities shown by metal allyl complexes.

Fluxionality in -allyl metal complexes

313
The complex Mn(CO)4 (3-C3H5) can exyhibit a rigid 'H n.mr. spectrum such as that
shown in Fig. 8.12.

The spectrum shown is of AA'BB'X type where, in the case of the 3-allyl metal
complex. X is the proton on the central carbon atom, A and A' are protons (quite different
from X) and are located anti to X, and B and B' are protons again quite different from X but
similar to A and A' and located syn to X. At elevated temperatures or in the presence of a
base, however, this spectrum collapses to a dynamic A4X spectrum, the chief feature of
which is change of the doublets for the A and B protons to a single doublet presumably
owing to a rapid (on the n.m.r. time scale) intramolecular rearragement that causes the A/A'
(anti) and B/B' (syn) protons to have the same chemical shift.

Trihaptoallyl-metal complex

Fig. 8.12.

314
This transition may be represented as follows :

Similar behaviour is seen in Cp2Hg. At normal temperature it shows presence of three


types of hydrogen (Fig.8.13.). However below – 700C all the hydrogens become equivalent.

Fig. 8.13.

During synthesis of cyclooctatetraene–metal tri carbonyls also fluxional behaviour


has been seen.

8.4. FLUXIONAL BEHAVIOUR IN DIENYL COMPLEXES

A few examples of this class of compounds are :

Fe(1-C5H5)2(5-C5H5);Cu(1C5H5)(PEt3);Si(1C5H5)Me3; Ge(1C5H5)2;

Me2, Sn(1C5H5)4; Cr(1=C5H5)(NO)2(5C5H5); Ti(-C5H5)2 (5-C5H5)2;

Re(1-C7H7)(CO)5,

315
The Compound Fe(1-C5H5)(NO)2(5-C5H5)(first synthesized by Piper and
Wilkinson in 1953) represents one of the first examples of fluxional organiometallic
molecules. The observation of two singlets in the 'H n.m.r. spectrum (at room temperature)
was considered to be highly unusual, because one would expect a singlet (for pentahapto
cylcopentadienyl ring) and a pair of doublets (for monohapto cyclopentadienyl ligand) or
triplets. Such observations in the 1H n.m.r. study of Fe(1-C5H5) (CO)2 (5-C5H5) and for
many other similar systems. (fig 8.14) led to a conjecture about a mechanism for
rearrangement reactions which could render all the monohapto bonded cyclopentadienyl
protons magnetically equivalent. The variable temperature. 1H n.m.r. spectrum of this
molecule (Fig. 8.15) over the range + 30oC to ─100oC provides valuable information. Some
characteristic features of the spectrum are: (i) the nature of the spectrum over the range
─80oC to ─100oC is almost unaltered (the limiting spectrum) and provides evidence
regarding the instantaneous structures in solutions, and (ii) recognition of rearrangement
pathway.

Fig. 8.14.
(a) NMR at -270C
(b) NMR at -620C

316
Fig. 8.15. The variable temperature 1Hn.m.r. spectra (at 60 HMz) of
Fe(1-C5H5)(CO)2(5-C5H5) in CS2
Although the plausible pathways for proton averaging may involve (i) a dissociative
mechanism, (ii) random shifts, (iii) 1,2-metal shift (i.e. movement of a metal atom around the
cyclopentadienyl ring from one carbon to the carbon α to it), or (iv) 1, 3-metal shift, yet the
experimental evidence favours the 1, 2-metal shift as the most appropriate mechanism (Fig
8.16)

Fig. 8.16. Proton averaging by 1.2-metal shift mechanism


For the recognition of the rearrangement pathway, generally the following points
have been considered to be of great value:
(i) The unsymmetrical collapse of the low field pattern (δ 5.8─6.4) eliminates
possibilities like random site exchange or a rearrangement process making all the
possibilities like random site exchange or a rearrangement process making all the sites
equivalent. This type of observation can in fact lead to only two possibilities, e.g., 1, 2-shifts

317
(but not a mixture of both). A close examination of the spectrum (Figure 8.14) permits one to
distinguish between the latter two pathways provided the two low-field complex multiplets
can be assigned;

(ii) Multiplets in the low-field may be described as AA'BB' resonance, the downfield side
of which is broadened more by interaction with allylic H compared to the upfield side; this
may be due to α-H atoms. It may be noted that assignment of α- and β-character on the basis
of chemical shifts is highly risky. However, magnitudes of coupling constants would be
fairly safe to indicate α- or β-character of the protons, e.g. α-protons would be coupled (with
a coupling constant value  2Hz) more strongly to allylic H than the β-proton (J0.5 Hz). In
view of the above, the downfield part of the multiplet, which collapses faster than the upfield
half, may be considered to have predominantly α-character, and the rearrangement pathway
would involve more frequent in and out movements of protons in the α-environments than in
the β-environment. It is easy to recognize that a succession of 1, 2-shifts causes redistribution
of protons among α-environments, twice as often as among β-environments (whereas 1, 3-
shifts have just the opposite effect).

An another important example is that of (5-C5H5)2 Fe2 (CO)4. At -70oC, the solution
of the complex show protons at two places in its 1H n.m.r/ spectra, which with the increase in
temperature converts into single strong signal (Fig 8.17)

Fig 8.17 1H n.m.r. spectra of (5-C5H5)2 Fe2(CO)4 at different temperatures.

318
13
C n.m.r. shows cis-trans exchange in this complex (Fig 8.18) between bridged and
terminal CO groups:

Fig 8.18

It appears that, an intermediate compound, from opening of CO to unbridged C5 H5


(CO)2 Fe-Fe (CO)2 C5 H5 is formed.

CHECK YOUR PROGRESS

Note: (1) Write your answers in the space given below.

(2) Compare your answers with those given at the end of this unit.

(a) (i) Fluxional behaviour may be define as ..............................................


...........................................................................................................
...........................................................................................................

(ii) In AB5 molecule the TBP structure changes to ...........................and again to


........................................ configuration.

(iii) The most important method for the study of fluxional behaviour is
......................................................................... .

(b) (i) In NMR spectra of Os (PPH3) (CO) (NO) (C2H4) at ........................ temperature
........................................... of resonance lines of equal frequency are obtained,
which at ...................................temperature is converted in
to.........................................

(ii) H.N.M.R. spectra of tetra-methyl alene carbonyl at -600C gives


..........................................which are due to ..................................... and

319
.................................. trans. hydrogen's and ............................... ............... placed
perpendicular to six C-Fe bonds. On increasing the temperature these are
change to ........................................... showing that .............................................

(iii) N.M.R. spectra of Ru (CO)3 (4-C8H8) complex indicates that .....


............................................structure is changed to ........................
configuration.

(iv) 3-allyl complexes, specially one ....................... complexes show


........................... n. m .r. spectra show these complexes are
................................... non rigid. At low temperature these are in AA'BB'X
configuration but at high temperature these are changed to ...........................
i.e. at low temperature of hydrogens are present, which
..................................... at higher temperatures.

(v) At normal temperature Cp2 Hg shows ..................................... types of


hydrogen's.

13
(vi) C-n m r spectra of (n5-C5H5)2 Fe (CO) indicates .........................
..................... exchange of ................................. and CO groups.

8.7 LET US SUM UP

After going through this unit you would have achieved the objectives stated earlier
in this unit. Let us recall what we have discussed so far:

 The molecules which have more than one thermally accessible structures, which
under suitable conditions (specially temperature) are interconvertible from one to
another fairly rapidly. This phenomenon may be termed as fluxional behaviour.

 First example of fluxionality was PF5 molecule. In 1953 Gutosvsky indicated


fluxionality in PF5. Berry in 1960 using n.m.r. studies indicated that the TBP structure
of PF5 change, through square pyramid structure, in to another TBP configuration in
which axial and equatoral fluorine atoms interchange their position. This

320
phenomenon was called berry`s pseudoratation.

 As the diffraction and spectral (1R, Visible, UV) methods are quite fast (~10-14 to
10-20s) compared to molecular vibration, hence these methods are not useful for the
study of fluxional behaviour of compounds.

 NMR. method was found quite useful in the study of fluxional behaviour of
molecules. In this method, changes in structures of n.m.r. lines, with the temperature
are analysed. Using this method fluxional of behaviour many organometallic
compounds has been studied e.g. 2-olefin complex, alene complex, π-bonded cyclic
alkene, complex.
3-allyl complexes and diene complexes.etc.

 NMR spectrum of Os (PPh3)2 (CO) (NO) (C2H5), at -900 C shows two sets of
resonance lines of equal intensity, but these coalesce to a broad signal at -650C.
Showing the two sets of hydrogen in different environments at -650C.

 Similarly, 'H-nmr spectrum of Fe (CO)3 (4-C8H8) at room temperature gives only


one line, which at low temperature splits in two broad signals This indicaties that the
two sets of hydrogen at low temperature become equivalent at room temperature,
confirming fluxional behavior of the molecule.

 Similarly, fluxionality in Ru (CO)3 (4-C8H8) and Os (CO)10 H(3-CH3 CH2 C = C


CH2 CH3) molecules has also been confirmed by using n.m.r studies

 3 allyl molecules are also stereochemically nonrigid molecules. At low temperature


this has AA'BB'X type structure indicating two sets of hydrogen in different
environments, which changes to XA4 type structure on increasing the temperature
showing that intermolecular change makes all hydrogen equivalent.

 At normal temperature Cp2 Hg shows three types of hydrogen in its n.m.r. spectra,
which changes, showing all hydrogen equivalent, at – 700C Similarly, 13
C-nmr
spectra of (5-C5 H5)2 Fe (CO) 2 shows that in the molecule there is cis-trans
exchange in between bridged and terminal CO-groups.

321
8.8 CHECK YOUR PROGRESS : THE KEY

(a) (i) The molecules which have more than one thermally accessible structures, which under
suitable conditions (specially temperature) are inter convertible from one to
another fairly rapidly This phenomenon is known as fluxional behavior.

(ii) SP (square pyramidal)

TBP

NMR

(b) (i) -900C two sets

-650C

a broad signal

(ii) three peaks

three cis

three

three hydrogens

single signal

all hydrogen are equivalent

(iii) 1,3

1,2

(iv) ligand

fluxional behavior

stereochemically

322
XA4

two sets

all become equivalent

(v) three

(vi) cis-trans

bridged

terminal

323