Metal Carbonyls

Periodic Table
Periodic Table

Sc Ti V Cr Mn Fe Co Ni Cu

3d elements
Homoleptic complexes

Sc Ti V Cr Mn Fe Co Ni Cu
No
complex [V(CO)6]- Cr (CO)6 [Mn(CO)5]- Fe(CO)5 Co(CO)4- Ni(CO)4 [Cu(CO)4]+

(1)  metal is usually in the zero oxidation

state.

(2) Coordination No. and geometry are

well defined and restricted.
•  Oxidation States and Coordination

(1)  metal is usually in the zero oxidation

state.

(2) Coordination No. and geometry are

well defined and restricted.
Survey of homoleptic complexes

Sc Ti V Cr Mn Fe Co Ni Cu
N o
complex [V(CO)6]- Cr (CO)6 [Mn(CO)5]
- Fe(CO)5 Co(CO)4- Ni(CO)4 [Cu(CO)2]+

No neutral complex X Mn2(CO)10 ? Co2(CO)8 X X

Survey of homoleptic complexes

Sc Ti V Cr Mn Fe Co Ni Cu
N o
complex [V(CO)6]- Cr (CO)6 [Mn(CO) ]
- Fe(CO)5 Co(CO)4- Ni(CO)4 [Cu(CO)2]
+
5

No neutral complex X Mn2(CO)10 Fe2(CO)9 Co2(CO)8 X X

3. EVEN NEGATIVELY CHARGED METAL COMPLEXES ARE FORMED!!

Empirical
18 electron rule
•  We noted that their complexes were
distinctly different from the Werner
complexes of NH3 and H2O ligands. They
are always 18 electron complexes.

•  Co3+ is a d6 complex and has [Co(H2O)6]3+

and is similar to the Cr3+ complex but
[Cr(H2O)6]3+ does not follow the EAN rule
•  Oxidation States and Coordination

(3) Another striking difference from

coordination complexs is the color and
magnetism of the complexes.

Except vanadium carbonyl; all of them

are colorless and diamagnetic.
Metal carbonyls form symmetrical structures !

Metal carbonyls may be mononuclear or polynuclear

 Multinuclear complexes
possible!
•  4. M-M bonds are rare and even if they are
multinuclear complexes due to oxo
bridges, they do not have M-M bonds.
M = Ru, Os
Bridging
5.  CO is found bridging in dimers and
trimers with great facility. Werner
ligands such as H2O and NH3 do
not form “dimers” like metal
carbonyls
Aggregation: multinuclear
complexes
5. Special bridging ligands “oxo”
“hydroxide” or azide etc. are
needed in Werner complexes, but
for CO both terminal and bridging
modes are facile
Mn2(CO)10 no bridges;
Co2(Co)8 - 2 bridges Solid State
Co2(Co)8 - no bridges in solution.
Fe3(CO)12 - 2 bridges
Fe2(CO)9 3 bridges
Ru3(CO)12 - no bridges
Physical Properties
•  Gases or liquids
•  Neutral compounds, unlike the Werner
complexes, have hydrophobic character.
•  Soluble in organic solvents.
•  Negatively charged species are stable!
Structure

(6) If one looks at the structure one finds

the M-C bonds are shorter than expected
for single bonds.

Fe - C Fe – C expected 2.2 Ang.

Fe - C 1.833 (eq) 1.810 (ax)
C–O distances are longer than free
CO by 0.01 ang.
Spectroscopy

(7)Spectroscopy (IR) which is very useful in

identifying the structures suggests the C – O
bond order in M -CO complexes are less than
in free

2143 cm-1 is the νC-O (C-O stretch is free CO).

In most CO complexes they are in the range

1850 – 2100 cm-1 .
Spectroscopy

9) In a few complexes, they are found to have

stretching frequency greater than 2143
cm-1 which is the stretching frequency for free
CO!
 Average bond enthalpy (Kcals / mol)

•  Cr 25 Mn 24 Fe 28 Ni 35

•  Mo 36

•  W 42 Re 45

•  As you go down the periodic table, the M-C bond

becomes stronger!
Synthesis of metal carbonyls
Synthesis of metal carbonyls
 Characterization of metal carbonyls

IR spectroscopy M-C-O
(C-O bond stretching modes)
 Characterization of metal carbonyls

IR spectroscopy M-C-O (C-O bond stretching modes)

Usefulness of IR spectra in identifying isomers
Usefulness of IR spectra in identifying isomers
 Can 13C NMR spectroscopy help ?
13C is a NMR active nucleus (S = ½)
chemical shifts ∼ δ 200-300 ppm
But the natural abundance is only 1%

Metal carbonyl complexes have very long T1

(using relaxation agents like Cr(acac)3

and long delay times can help)
Why do they form?
–  Metals have heats of vaporization
= 200-400 kJ/mol
•  VERY DIFFICULT TO GET
ISOLATED “M”

•  M solid ---! M gas

•  Only for Ni metal, one can pass CO

gas and react the two species to
form the carbonyl complex …
•  Iron, will also form the complex, if
“iron” is extra pure!
Why do they form?
–  CO is a stable molecule small
dipole moment, C –ve
–  Heats of formation (110 kJ/mol)
–  Protonation
•  Analog of nitrogen one of the most
inert molecular species known.
•  Theory estimates 70-100 Kcal / mol
BDE for M-CO and 0.02 Å Shorter
bond!
Structural Parameters
•  If one looks at the structure one finds the M-C bonds are shorter
than expected for single bonds.
Fe - C Fe – C Fe – C(sp) (1.43 + 0.67)
1.810, 1.833 2.10 A

C – O distances are longer then C – O in CO! (1.128 Α)%

•  Usually between 1.14 and 1.16

 Spectroscopy

•  Spectroscopy (IR) which is very useful in

identifying the structures suggests the
C – O bond order in M CO complexes is
less than in free CO

•  (2143 cm-1 is the C-O stretch is free CO).

In most CO complexes they range from
1850–2150 cm-1 .
Molecular Orbitals σ C---O
Molecular Orbitals

C---O
 Key Features
•  18 electron complexes dominate!
•  Neutral metal atoms and not ions as in
Werner complexes
•  CO can bridge and form terminal
bonds
•  M-M bonds are possible and stable
•  Best explanation is the
DCD model of give and take!
•  A general phenomenon!
Metal&Carbonyl&Complexes&

Bonding&in&organometallic&chemistry&
 Key&Features&of&the&Unique&CO!&
•  18&electron&complexes&dominate!&
•  Neutral&metal&atoms&and&not&ions&as&in&
Werner&complexes&
•  CO&can&“bridge"&and&form&terminal&bonds&
•  MEM&bonds&are&possible&and&stable&
•  Spectroscopy,&chemistry&and&structural&
features&have&to&be&explained!&
•  Any$model$of$bonding$should$account$for$
all$the$above$factors!$
Structural&Parameters&
•  If&one&looks&at&the&structure&one&finds&the&MEC&bonds&are&shorter&than&
expected&for&single&bonds.&
&Fe&E&C&&&&&&&Fe&–&C& &&&&&&&&&&&Fe&–&C(sp)&&&&(1.43&+&0.67)&
&&&&&&1.810, &&&&&&&1.833&&&&&&&&&&& & &2.10&A&&
&
&&&C&–&O&distances&are&longer&then&C&–&O&in&CO!&(1.128&Α)"

•  &Usually&between&1.14&and&1.16&
 Spectroscopy&

•  Spectroscopy&(IR)&which&is&very&useful&in&
iden[fying&the&structures&suggests&the&&
&C&–&O&bond&order&in&M&CO&complexes&is&less&
than&in&free&CO&&

•  (2143&cmE1&&is&the&CEO&stretch&is&free&CO).&&
&In&most&CO&complexes&they&range&from&1850–
2150&cmE1&.&&
 Back&bonding,&da[ve&bonding,&DCD&
model&of&bonding,&….&
•  The&DCD&model&of&“give&and&take”&of&
electrons!&&best&model&that&explains&all&facts.&&

•  :CΞO:&donates&a&pair&of&electrons&to&the&metal&
•  M&gives&a&pair&of&electrons&to&the&CO&π*&
Molecular&Orbitals&&σ& CEEEO&
 CEEEO&
Molecular&Orbitals&
Evolu[on&of&Cr&Orbitals&in&Cr(CO)6&

n+1$$$p$

n+1$$$s$

nd$
MECO&interac[ons&
 BackEbonding&
•  &π&bonding&

•  Electron&dona[on&decreases&CO&stretching&
frequency.&
•  Increases&the&CEO&bond&distance&
 How&do&we&establish&synergis[c&
bonding?&
•  &σ+π&bonding&

&
Effect of charge
 How&important&is&this&back&bonding?&
•  This&should&be&sta[s[cally&significant!&

•  Database$Analysis$of$Transi<on$Metal$Carbonyl$Bond$Lengths:$
Insight$into$the$Periodicity$of$π!Back&Bonding,!σ!Dona.on,!and!the!
Factors$Affec<ng$the$“Electronic$Structure”$of$the$TM=C=O$Moiety$
$
Rosalie&K.&Hocking,&and&Trevor&W.&Hambley&
Centre&for&Heavy&Metals&Research,&School&of&Chemistry,&University&of&Sydney,&
Sydney,&&NSW&2006,&Australia&

•  Organometallics&2007,!26,!2815&2823!&
Expect&a&nega[ve&correla[on&in&the&
Å$
TMEC&&vs&&CO&bond&length&

Å$
 TMEC&&vs&&CO&bond&length&

1.25&Å&
4d,&5d&TMECO&
CEO&bond&length&

1.20&Å&

1.15&Å& 3d&TMECO&
CO&gas&
1.13&Å&

1.10&Å&

1.05&Å&

1.65&Å& 1.80&Å& 2.05&Å& 2.15&Å& 2.25&Å&

MEC&bond&length&&
 How&mul[ple&effects&affect&the&TMEC&&
and&&CO&bond&lengths&
4%& 6%&
1.25&Å&
&π&is&more&imp!&

1.20&Å&
CEO&bond&length&

1.15&Å& σ&&and&π&
CO&gas&
1.13&Å&

1.10&Å& &σ&is&more&imp!&

1.05&Å&

1.65&Å& 1.80&Å& 2.05&Å& 2.15&Å& 2.25&Å&

3d&transi[on&metal&–&C&distances&in&MECO&
Mul[ple&effects&will&result&in&
nonElinear&rela[onships&
•  π&&bonding&:&dona[on&of&electron&
density&to&the&an[Ebonding&orbitals&
of&CO!&
–  Reduces&CO&bond&order&

•  σ&bonding&:&&&dona[on&of&electron&
density&to&the&transi[on&metal&atom.&
–  Will&discuss&this&later..&
 More&proof&that&π&is&important&
•  &π&bonding&is&shared&by&trans&ligands&

•  Electron&dona[on&ability&decreases&
CO&stretching&frequency&in&the&trans&
posi[on.&
•  &π&bonding&is&shared&by&trans&ligands&

•  Ability&to&withdraw&electrons&by&the&
trans&ligand,&increases&CO&stretching&
frequency!&
•  &π&bonding&is&shared&by&trans&ligands&

•  Ability&to&donate&electrons&by&the&
trans&ligand,&decreases&CO&stretching&
frequency.&Increases&the&MECO&bond&
strength&
Examples&of&the&influence&of&trans&
ligand&in&a&Ir(CO)2L2&complex&
Examples&of&the&influence&of&trans&
ligand&in&a&Rh(CO)2L2&complex&
“Chemical”&evidence&for&π&bonding&
•  Reac[on&of&Cr(CO)6&should&lead&to&
cis&subs[tu[on&if&the&ligand&is&a&π&
donor.&
•  If&this&is&the&case,&one&would&
expect&reac[on&with&2&equiv.&of&
Me3N&to&give&cis&subs[tu[on!&&
•  More&than&two&should&give&the&
“fac”&isomer!!!&
 Influence&of&trans&ligand&
Spectroscopic&Evidence&

Effect of other ligands

A&series&of&fac&complexes&can&be&examined&
M(CO)3(PR3)3&

Electronega[vity&of&the&subs[tuent&on&PR3&affects&CO&stretch&
 Let&us&discuss&the&σ&
•  π&&bonding&:&dona[on&of&electron&
density&to&the&an[bonding&orbitals&of&
CO!&
–  Reduces&CO&bond&order&
•  σ&bonding&:&&&dona[on&of&electron&
density&to&the&transi[on&metal&atom.&
–  How&does&this&affect&CO&?&
Improves&CO&bond&order&and&shortens&
the&CO&bond&length.&
•  HOMO&is&slightly&an[Ebonding..&
•  Charge&effect&/&not&due&to&the&sigma*&
nature&of&donor&orbital&on&CO!&
 EAN&
Necessary&but&not&sufficient&
•  Complex&of&Ni&d10&has&[Ni(CO)4)].&&
•  And&Zn2+&is&d10&but&does&not&form&a&similar&
complex.&

–  Does&not&bind&CO!&
–  has&an&octahedral&geometry&with&water&
–  and&is&not&similar&to&Ni(0)&in&Cord.&No.&and&
geometry.&
 Strauss&Complexes..&
•  [Hg(CO)2]2+&&&&&stretching&frequency&is&2278&cmE1&
•  [Pd(CO)4]2+&&&&&stretching&frequency&is&2248&cmE1&

•  IR&Spectroscopy&(which&is&very&useful&in&iden[fying&the&mode&of&binding)&suggests&
that&the&C&–&O&bond&order&in&MECO&complexes&is&less&than&what&is&observed&in&free&
CO&&
•  In&most&CO&complexes&they&range&from&1850–2150&cmE1&&&
•  2143&cmE1&&is&the&CEO&stretch&in&free&CO.&&In&CO+&&&2214&cmE1&
&
&&&&
&C&–&O&distances&are&longer&than&C&–&O&distance&in&free&CO!&(1.128&Α)"
•  &It&is&Usually&between&1.14&and&1.16&in&neutral&/&nega[vely&charged&carbonyl&
complexes.&

•  However,&in&these&+vely&charged&complexes,&the&CO&distance&is&shorter!&&
–  (Interes[ngly,&in&CO+&&&&&&&&CEO&dist&is&1.115&ang.&)&
•  Back&dona[on&is&not&important&or&significant!&

•  Nature&of&5σ&orbital.&Is&it&an[&bonding?&
•  Why&CO&frequency&goes&up&in&[M(CO)]+&&
Molecular&Orbitals&

+& CEEEO&
•  CO&is&rarely&found&bonded&to&Mn+&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& & &&
•  In&&complexes,&where&they&are&bound&to&&they&have&a&CO&stretch&that&&is&
greater&than&2143&cmE1&which&is&the&stretching&frequency&for&free&CO&
&
•  Alternate&sugges[on&to&explain&this&feature&is&that&given&by&Frenking&&&
Strauss.&

•  &A+ve&charge&next&to&CO&makes&CO&bond&stronger&by&polarizing&the&π&cloud&
to&resemble&that&of&N2!&

•  Frequency&goes&up&in&H3BECO&because&B&is&+ve!&
–  CEO&stretch&is&2164&cmE1&&&&
–  BEC&bond&is&quite&strong.&23&&&Kcals&/&mol&&&&&&&&&&&&&&&&&&&&&&
–  It&is&not&just&an&electrosta[c&interac[on!&&&&&
 One&more&reason&why…&
•  Why&C&end&of&CO&is&bound&to&metal&atoms.&
 Reduced&Repulsion&in&MECO&
•  The&explana[on&for&CO&bonding&to&the&metal&
through&C&is&more&than&just&the&nature&of&5&σ"
•  What&we&have&is&the&π and&π*&&having&the&
same&symmetry.&
•  t2g&orbitals&can&interact&with&both&of&them.&
•  π interac[on&is&destabilising.&Thankfully,&the&
overlap&is&small.& π overlap&is&large&and&it&is&
stabilising.&
"
 Key&features&of&MECO&bonding&
•  Bever&bonding&by&donor&orbital&of&CO&pointed&
towards&the&M&through&C!&
•  Bever&π&acidity&of&CO&can&be&realized&if&C&is&
pointed&towards&the&M!&
•  Reduced&repulsion&from&the&filled&orbital&of&
CO&and&the&filled&M&orbitals&if&C&in&CO&is&next&
to&M&
•  Charge&effect&polarizes&the&C&making&it&more&
electronega[ve(!).&Makes&CEO&bond&stronger.&
 Key&effects&of&MECO&π&bonding&
•  π&acidity&of&CO&makes&the&MEC&bond&have&a&
double&bond&character.&&
•  π&acidity&of&CO&transfers&excess&electron&
density&on&the&metal&to&the&CO&π&*,&supports&
nega[ve&oxida[on&states.&
•  π&acidity&of&CO&uses&a&d&orbital&on&the&metal&
that&interacts&with&the&trans&ligand.&Trans&
ligand&should&be&a&weaker&π&acid&or&bever&it&
should&be&a&π&donor.&
 Based&on&what&we&have&studied..&
•  Draw&the&structures&of&metal&
carbonyls&
–  Iron&carbonyl,&triEiron&carbonyl&
–  Ru3(CO)12&
•  Arrange&in&the&order&of&increasing&CO&
frequency:&
–  Ni(CO)4,&Co(CO)4E&and&Fe(CO)42E&
•  &Predict&bond&distance&changes&in&CO&
complexes!&
•  Stability&of&isomeric&carbonyl&
complexes&&
 Key$Features$
•  18$electron$complexes$dominate!$
•  Ca8ons$as$in$Werner$complexes$form$
weak$bonds$to$CO.$
•  Bond$order$to$CO$like$ligands$is$more$than$
one!$
•  Best$explana8on$is$the$$
$DCD$model$of$give$and$take!$
•  A$general$phenomenon,$not$based$on$
isolated$examples!$$
 Key$effects$of$MICO$π$bonding$
•  π$acidity$of$CO$makes$the$MIC$bond$have$shorter$
MIC$bonds$than$expected.$$
•  π$acidity$of$CO$transfers$excess$electron$density$
on$the$metal$to$the$CO$π$*,$supports$nega8ve$
oxida8on$states.$
•  π$acidity$of$CO$uses$a$d$orbital$on$the$metal$that$
interacts$with$the$trans$ligand.$For$a$strong$MICO$
bond,$the$trans$ligand$should$be$a$weaker$π$acid$
or#even#be(er,$it$should$be$a$π$donor.$
•  CO$can$bridge$and$form$terminal$bonds$
•  MIM$bonds$are$possible$and$stable$
Evolu8on$of$Cr$Orbitals$in$Cr(CO)6$

n+1###p#

n+1###s#

nd#
 Orbitals$in$Cr(CO)6$

6#π*CO#
d2sp3#
6#π*CO#

6#CO#lp#### d3#

6#πCO#
6#πCO#
 Orbitals$in$Ni(CO)4$

4#π*CO# sp3#
4#π*CO#

4#CO#lp#### d5#

4#πCO#
4#πCO#
 Orbitals$in$[PtCl4]2I$

dsp2#

4#Cl#lp#### d4#

4#πCl#
4#πCl#
 18$electron$rule$
•  Electron$Coun8ng$$$$(electrons$are$not$tagged)$

•  2$Methods.$$
–  Ionic$method$
–  Neutral$method$

$
 Neutral$method$
•  H3CI$,$C6H5I,$C2H3I,$HICCI,$$$$
•  IR$
7
•  ClI,$NO2I,$N3 ,$O=NI$(BENT)$
•  C3H5I$ONLY$ONE$CARBON$IS$ATTACHED$TO$THE$METAL$

•  CO,$PPh3,$$
•  C2H4,$

•  NO$$(linear)$$3$ELECTRON$DONOR$
•  C3H5I$$$$3$CARBONS$ARE$ATTACHED!$$$
 IONIC$METHOD$
•  H3CI$,$C6H5I,$C2H3I,$HICCI,$$$$
•  IR$
•  7
ClI,$NO2I,$N3 ,$O=NI$(BENT)$
•  C3H5I$ONLY$ONE$CARBON$IS$ATTACHED$TO$THE$METAL$
•  CO,$PPh3,$$
•  C2H4,$
•  NO$$(linear)$$$
–  2$ELECTRON$DONOR$+1$CHARGE$
•  C3H5I$$$$3$CARBONS$ARE$ATTACHED!$$
–  $4$ELECTRON$DONOR$I1$CHARGE$
 Orbitals$in$Cr(CO)6$

6#π*CO#
d2sp3#
6#π*CO#

6#CO#lp#### d3#

6#πCO#
6#πCO#
 Bonding$in$CO$
–  $σ$bonding$ –  $π$bonding$
 Shared$orbitals$bond$order?$
•  $σ+π$bonding$

$
 Trans$influence$

Nitrogen$is$a$good$donor$
S$a$poor$donor$$
Trans$influence$
 Photochemical$Ac8va8on$Cr(CO)6$

6#π*CO#
d2sp3#
6#π*CO#

6#CO#lp#### d3#

6#πCO# Bonding$orbital$is$depleted$of$electron$density$
6#πCO# An8bonding$orbital$is$populated$
MICO$bond$is$weakened$
Easy$to$oxidize$and$easy$to$reduce!!$
 Photochemical$ac8va8on$of$
dissocia8on$
•  Cr(CO)6$$$$$$$$$$$$$$hν$$$$$$$$$$$$$$$Cr(CO)5$$$$+$$CO$
Radical$ac8va8on$
Electrochemical$ac8va8on$
 Thermal$dissocia8on$
•  Cr(CO)6$$$$$$$$$$$$$$heat$$$$$$$$$$$$$$$Cr(CO)5$$$$+$$CO$

•  Cr(CO)5$$$$$+$L$$$$$$$$$$$$$$$$$$$$$$$$$$$Cr(CO)5L$

•  L$should$be$a$weaker$π$acceptor$110oC$$
Thermal$dissocia8on$
 Thermal$dissocia8on$of$metalImetal$
bonds$
•  Fe2(CO)9$$$$$$$$$$$$$$$$$$$$$$$$$$$Fe(CO)5$+$Fe(CO)4$

•  Styrene$$+$$Fe(CO)4$$$$
 Oxida8ve$cleavage$of$MIM$bonds$
•  Mn2(CO)10$$+$Br2$$$$$$$$$$$$$$$$$$$$$$$$$BrMn(CO)5$$
 Chemical$oxida8on$of$the$ligand$
•  M=C=O$$+$Me3NIO$$$$$$$$$$$$$$$$$$$$I$MIIC=O$
•  $$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$O$ N+Me
3 $

$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$$CO $$+$Me N$
2 3
 Ceric$ammonium$nitrate$
•  Ce+4$$powerful$one$electron$oxidant.$Destroys$
all$metal$carbonyls$

•  M(o)$$oxida8on$state$$$!$Mn+$
 Based$on$what$we$have$studied..$
•  Draw$the$structures$of$metal$carbonyls$
–  Iron$carbonyl,$triIiron$carbonyl$
–  Ru3(CO)12$

•  Arrange$in$the$order$of$increasing$CO$frequency:$
–  Ni(CO)4,$Co(CO)4I$and$Fe(CO)42I$

•  $Predict$bond$distance$changes$in$CO$complexes!$

•  Predict$rela8ve$stability$of$isomeric$carbonyl$
complexes$$
Iden8fy$the$metal$in$the$carbonyls!$

Which$is$the$correct$
Structure?$
 To$think$about….$
•  Fluxional$behaviour$
•  Difference$in$3d$and$4d$complex$structures..$
•  Bonding$in$triply$briding$M3CO$
•  Large$metal$clusters$$
Alternatives to CO
 CO An unique ligand

•  Most unusual π acceptor

–  (emphasized in text books)
 CO An unique ligand

•  Not a great donor but σ donation is

important.
 CO An unique ligand

•  Most unusual π acceptor

–  (emphasized in text books)
•  Not a π donor
–  (more important fact is ignored) C O
•  Unique features are the result of
electronegativity difference
between C and O
 Tweaking / Tuning CO
•  It is obvious that the electronegativity difference
between C and O is the key factor making CO a
good ligand.
Periodic Table
 Alternatives to CO

•  Trivial alternatives
–  CS,
–  CSe,
–  CTe
 Tweaking / Tuning CO
•  It is obvious that the electronegativity difference
between C and O is the key factor making CO a
good ligand. C has EN value of 2.55 and O has a
value of 3.44 on the Pauling scale.

•  When we go down the O group, we loose this

advantage. S, Se, Te are not very electronegative.

•  S has 2.58
•  Se has 2.55
 Alternatives to CO

•  Trivial alternatives
–  CS, CSe, CTe

–  SiS, SiSe, SiTe

–  Or even GeSe ?
–  Or Sn Te
 Tweaking / Tuning CO
•  To keep up the electronegativity difference, we
can change C to Si! Will it solve this problem?
–  The ability of Si to form π bonds decreases!
–  So Si=O is not expected to be a good ligand !

–  A second complication is the inert pair effect. This sets

in at Sn. So instead of a valency of 4, the Sn(II) state is
quite stable

•  In reality, only CS, CSe, CTe

are reasonable substitutes.
 Synthesis of CS complexes
Ph 3P S +
Cl
Ph 3P CS2 C
-
Rh Cl
Rh
Ph 3P S + PPh3

Ph 3P PPh3

Ph
Ph 3P S
P
C
+S Ph
Rh Ph
Ph 3P Cl
 Synthesis of CS complexes
•  Two other sources for CS
S=CCl2 Thiophosgene (dangerous stuff)

S=CCl(OEt) (equally dangerous)

 Synthesis of CS complexes
•  Two other sources for CS
–  CSCl2 Thiophosgene (dangerous stuff)
Synthesis of CS complexes
EtOC=SCl2 ethyl clorothioformate
 A thiocarbonyl complex with CO
Dicarbonyl-thiocarbonyl-tris(trimethylphosphite)-chromium

DETGEO

Cr-CO 1.836
Cr-CS 1.782
 An Ir thiocarbonyl complex with CO

TCTPIR

Ir-CO 1.945
Ir-CS 1.863
A Cr complex with CO and a
bridging thiocarbonyl!
 A ruthenium complex with a CS
and a carbene

USEXAS
 Spectroscopic features of CS
complexes
•  C=S stretching frequency
•  1200 to 1300 cm- 1
Synthesis of CSe complexes
 Structure of a Cr-CSe Complex

•  1.78 Cr-CSe
•  1.89 Cr-CO
 Alternatives to CO

CO

CN- Change O to N; it has one less electron

so add an electron to CN
CN R (CN- and H+ , a proton does not change
electron count, it only removes –ve charge)
+ N has one more electron than C: so remove it!
NO

BF Subtract one electron, add one electron!

BO-

BOR Recent paper {Chem.Eur.Jnl.1998,p.210}

 Alternatives to CO

CO

CN- Change O to N; And add one more electron

so add an electron to CN
CN R (CN- and H+ , a proton does not change
electron count, it only removes –ve charge)
+ N has one more electron than C: so remove it!
NO

BF Subtract one electron, add one electron!

BO-

BOR Recent paper {Chem.Eur.Jnl.1998,p.210}

 Alternatives to CO

CO

CN- Change O to N; And add one more electron

so add an electron to CN
CN R (CN- and H+ , a proton does not change
electron count, it only removes –ve charge)
+ N has one more electron than C: so remove it!
NO

BF Subtract one electron, add one electron!

BO-

BOR Recent paper {Chem.Eur.Jnl.1998,p.210}

 The cyanide ligand as an alternative to the carbonyl

Metal cyanides are hardly considered Organometallics

however they do have a M-C bond!
Reason:
CN – Stabilises many high oxidation states
like classical ligands
3−
[ Fe(CN ) 6 ]

Neutral metals are rarely stable with CN –.

A RARE example is:

4−
[ Ni (CN ) 4 ]
 Dicarbonyl-tetracyano-iron(ii)

ACAKOF
RNC is the neutral equivalent of CN-

R can be changed at will. Steric and electronic effects can

be explored.

In principle RNC can be a more useful ligand than CO.

- Cr, Fe,Co, Ni form homoleptic complexes with RNC just

like they do with CO

For preparing the Ni Complex, just start with Ni(CO)4

 ⊕ ( −)
R–N=C↔ R–N ≡C Better donor.
If they replace CO in Ni(CO)4 Are they better ligands than CO?
Yes at least for +vely charged systems
[Pt(CNR)4]2+

Thus one can make…Pd2+ and Pt 2+ complexes. They stabilise M in

positive oxidation states, but the complexes are very reactive towards
nucleophiles. They attack the ligand at C
 Alterna(ves+to+CO+

+C+ligands+with+a+M5C+π+bond++
C5Ligands++
C+Ligands+with+π+character+
C+Ligands+with+π+character+
 π+character+of+Ar5NC+
.+
5 +IR+Stretching+frequency+for+three+systems+(in+cm51)+

Lν N ≡C − 2136 For+free+ligand+Ar#–#NC#(paratolyl)+
+
Back+bonding+from+metal+to+the+ligand+is+
L4 Ni − 2036 present;++stretching+frequency+is+lowered.+

Just+like+CO,.+If+the+M+is+++charged.+
L4 Ag ⊕
− 2186 +there+is+no+back+bonding!+
 :
R+–+N+=+C+ ↔+ +R+–+N++
⊕
≡ C (− ) BeSer+donor.+

They+replace+CO+in+Ni(CO)4+++
Are+they+beSer+ligands+than+CO?+
Yes+++++++++++++++++++++++++++++++++++++At+least+for++vely+charged+systems+

[Pt(CNR)4]2++

Thus+one+can+make…Pd2++and+Pt+2++complexes.++
The+ligands+stabilise#M+in+posi(ve+oxida(on+states,++
like+CO+stabilizes+zero+oxida(on+state!+++
But+the+complexes+are+very+reac(ve+towards+nucleophiles.++
Nucleophiles++aSack+the+ligand+at+C#
Reac(vity+of+RNC+Ligands+

R+=+Et+
+
Alterna(ves+to+CO+
+
+ +
CS,+CSe + + +CS+and+CSe+are+very+good+ligands.+
+
+ +Based+on+M5C+bond+lengths,+they+are+as+good+as+CO+
+ +Difficulty+in+making+them+is+quite+high!!+

+CN
5+++++ +Change+O+to+N;+And+add+one+more+electron++
+ + +so+adding+an+electron+to+CN+gives+a+ligand+like+CO!+
++
RN=C+++++++ + +Forms+very+good+complexes+but+hydrolysed+easily!+
+
+
C(NR2)(OR)++++++
C(OR)2+++++++
C(NR2)2+++++++++
+
+
CR2+++
 NHC+

Hetero+atom+stabilized+cyclic+carbene+
complexes+
ASempted+prepara(on+of+carbene+
Prepara(on+of+a+carbene+
complex!+
H H H
N N N

+ Fe(CO)5 Fe(CO)4

N N
N H H
H
Another+carbene+prepara(on+
When+subs(tuent+at+N+is+bulky,+
the+species+could+be+isolated.+In+
this+example+it+is+adamantyl+
Arduengo+(1991)++
+
5NaX+
Mesityl+instead+of+adamantyl+
was+good+enough.+
+
dimethyl+phenyl+could+also+be+
prepared!++
+
 Structure+of+the+carbene+
NR N
The image cannot be displayed. Your computer may not have enough memory to open the image, or the image may have been corrupted. Restart your computer, and
then open the file again. If the red x still appears, you may have to delete the image and then insert it again.

+
C H NaH(DMSO) C

THF solvent
5
NR N
X +

R R

+
N: N:

-
C C -
Aromatic Species!
6 π electrons N: N: +

R R
Ease+of+prepara(on+from+the+
imidazolium+salt+
 N N
R R N N
S R R
Imidazolium+salt+
Deprotonated+salt+gives+a+carbene!+
Space+filling+model+of+the+carbene!+
 N5heterocyclic+carbenes+
can+be+complexed+to+a+metal!+
+
R

R
 N5heterocyclic+carbenes+
can+be+complexed+to+a+metal!+
+
 N5heterocyclic+carbenes+
can+be+complexed+to+a+metal!+
+
Synthesis+of+a+Pd+complex+
 ++
Ad Ad Ad

N N N

C
+
H
Hg(OAC)2 + +
C Hg C
- 2 AcOH
N N N

Ad
X
5+ Ad Ad

Ad Ad

X
5+
N N OC
CO
C
+
H
HCr(CO)5- +
C Cr-
CO
- H2 OC
N - N
X CO

Ad Ad
Geometrical+Changes+in+NHC+
 Strong+sigma+dona(on;+poor+pi+
acceptor+
Cr(CO)6+ Raman+stretch+2108+cm51+

+ -
Cr (CO)5
υ+CO+trans+to+NHC+carbene+:++1972+cm51+
N
R

H3C

Cr(CO) 5 υ+CO+trans+to+carbene+:++1953+cm
51+

H3C O
 Quan(fying+Electronic+Effects+
•  BeSer+to+look+at+a+series+of+complexes.+

•  Tolman+did+this+with+[Ni(CO)3(L)]+where+the+L+is+a+NHC.+
He+quan(fied+the+symmetric+stretch+of+the+3+CO+
ligands+as+a+func(on+of+L+

•  L+=+CO+++TEP+is+2060+

•  The+average+CO+stretch+is+called+the++
+++++Tolman+electronic+parameter.+(TEP)+++
+
 Electronic+Proper(es+

TEP+in+Cm51+++++++2060++++++++++++++++++++2061+++++++++++++++++++++++2065+
 A<rac=ve#Features#of#NHC#
Electronic character
N5Heterocyclic+Carbenes++5+ +electron+rich,+neutral+σ5donors+

IR#values#of#the#carbonyl#stretching#frequencies#in#LNi(CO)3#measured#in#CH2Cl2#

Ligand# υco#(A1)#[cm91]# υco#(E)#[cm91]#

+ + +
Imes+ 2051+ 1970+
Ipr+ 2052+ 1970+
SIPr+ 2052+ 1971+
PCy3+ 2056+ 1973+
P(tBu)3+ 2056+ 1971+
PPh3+ 2069+ 1990+
ICy+ 2049+ 1965+

Benzimidazole#<#imidazole#<#imidazoline#
28+
Electronic+proper(es+
Tolman+Electronic+Parameter+

2040+
2055+ 2050+ 2048+ 2045+
Tuning+the+electronic+proper(es+
The+difference+in+the++
TEP+values+between+the++
Oxidized+and+reduced++
Forms+is+usually++
11513+cm51+
The+TEP+difference+
between+PPh3+and+PCy3+
is+also+similar+
 Electronic+Character+of+NHC+
•  13C+chemical+shiq+in+a+Pd(II)+complex+is+used+as+a+

probe.+Chemical+shiq+increases+with+NCN+angle+

Usually+on+complexa(on,+the+
chemical+shiq+goes+upfield+
by+30+ppm.+180+ppm.+
 Steric+
Features+

M5C+bond+length+2.0+Angstroms+

3.5+angstroms+
 NHC+CARBENE+
•  A+neutral+ligand+with+π+acceptor+capability+
•  Very+good+sigma+dona(on+
•  Tunable+electronic+and+steric+property+
•  Ligand+is+easily+synthesized+in(situ(
•  NHC#are#super#heroes!#
CARBENE'and'CARBYNE'

M=C'
M'''C'
C'Ligands'with'π'character'
Stable'carbenes'and'their'complexes'
'
1.  Stability'through'steric'protecDon'
2.  Stability'through'conjugaDon'
3.  Complexes'stabilized'because'of'π'acidity'.'
4.  Stability'through'aromaDcity'
'
Abnormal'carbene'complexes!'
SCIENCE''2009'VOL'326,'page'556''
www.sciencemag.org'
Molecular views of imidazolium bromide 6 (Br–) (left) and aNHC 9 (right) in the solid state
(Only the ring hydrogen atom is shown).

E Aldeco-Perez et al. Science

2009;326:556-559
 NHC'CARBENE'
•  A'neutral'ligand'with'π'acceptor'capability'
•  Very'good'sigma'donaDon'
•  Tunable'electronic'and'steric'property'
•  Ligand'is'easily'synthesized'in#situ#
•  NHC$are$super$heroes!$
•  aNHC$can$also$be$synthesized!$
Fischer'and'Schrock'Carbenes'
ReacDvity'of'the'central'“C”'towards'
nucleophiles'
'
Abnormal'NHC'are'stabilized'by'only'
one'hetero[atom'
FISCHER'CARBENE'

R = Bu
 O
C O
C O Cr-C distance = 2.04
O C Cr C
predicted from Cr+C = 2.21 0.77'+'1.44'Å'
R
C
C
O
O
O=C - 1.44 A expected for a double bond
1.33 A observed

O O
C O C O
C O C
O
O C Cr C O C Cr C
C R C R
C C
O O
O O

X-ray shows that both are

shorter than expected. 1
H NMR shows two isomers
are present and they
13
C NMR shows they have correspond to cis and trans
C=O double bond!
carbenium ion character C+
350-250 ppm
 FISCHER'CARBENE'
A'brief'look'at'the'bonding'in'these'complexes'
'
'
R

O
R

Two'fronDer'(valence')'orbitals'are'there!'
One'has'2'electrons'and'the'other'has'none!'
'
FISCHER'CARBENE'
Carbene'from'an'metal[ketyl'complex'
Carbene'from'an'alkyl'complex'
hν''Light!!'
''
C'''' M'
Is'there'some'way'to'have'strong'U=C'?'
NHC'complexes'with'lanthanide'and'uranium'complexes'with'NHC'are'known'
They'are'simple'Lewis'base'adducts'without'M[C'double'bond'character'
'
'Arnold,'P.'L.;'Liddle,'S.'T.'Chem.#Commun.#2006,%3959.%%
% C X
Giesbrecht,'G.'R.;'Gordon,'J.'C.'Dalton#Trans.#2004,%2387.'
''''
'
M'
'
'
How'do'you'get'around'this'problem?'
Make'both'bonds'have'electrons'flow'in'the'direcDon'of''
From'the'ligand'to'the''metal'!''
'
'

C'''' M'
 M=C'when'M'is'an'f[element'

R2C28$
 J.%Am.%Chem.%SOC.%1981,%103,%358963590'

Some Bond Lengths (Å) with Their Standard Deviations

Bond$Length$(Å)$
U8C(1)$ 2.29$(3)$
P8C(1)$ 1.69$(3)$
P8C(2)$ 1,83$(3)$
P8C(3)$ 1.83$(3)$
P8C(11)$ 1.80$(2)$
U8Cpa$ 2.79$(3)$
a - Average U-C distances for the 15 carbons of the C H rings
5 5

U[C'''2.6''Å expected

Rare U-CO complexes

U-C distance is 2.44'
Carbynes'
Carbynes'
 1.85'Å'

Churchill.%M.%R.,%%Inorg.%Chem.,$1979,$18$(1),$171–176$
Carbynes'
Carbynes'
•  We'have'looked'at'several'compounds'where''
the'M'is'bonded'to'the'C.'
•  The''bond'order'has'changed'from'1'to'2'to'3!'

•  Is'it'possible'to'have'C'as'a'ligand?'
'
Structure'of'a'carbide'complex!'
•  We'have'looked'at'several'compounds'where''
the'M'is'bonded'to'the'C.'
•  The''bond'order'has'changed'from'1'to'2'to'3!'

•  Is'it'possible'to'have'C'as'a'ligand?''
'
•  Is'it'possible'to'have'C'with'a'quadruple'bond'
to'the'metal?'
C'Ligands'with'π'character'
 Key'Points'
•  Carbon'can'have'mulDple'bonds'(1,'2,'or'3)'
with'the'metal'
•  The'bonding'could'be'synergisDc'as'in'the'DCD'
model''OR'it'could'be'one'way'
•  If'the'ligand'is'stable'in'the'free'state,'it'is'
easier'to'make'molecules'and'study'them.'
Otherwise,'one'can'always''generate'it'in'the'
coordinaDon'sphere'of'the'metal!'
Phosphorus(III) Ligands

Alternatives to CO
Good Supporting Ligands
ORGANOMETALLIC
CHEMISTRY

M-C
Overview of Ligands
C-Ligands
Non-C Ligands
 Advantages of P(III) Ligands
•  Phosphorus in oxidation
state(III); A pair of electrons
on P can be donated to the
metal.

•  Reaction PX3 with RMgX will

make PR3

•  Can be done stepwise.

 Characterization of P(III)
Ligands
•  X-ray crystallography of PPh3 complexes
is very common.
•  31P NMR spectroscopy is possible &
useful
•  IR spectroscopy is of little use
 Spectroscopy of 31P

•  31P
NMR is very useful but it is an
empirical tool.
•  Coordination to the metal usually shifts
MOST ligand signals upfield.
–  But 31P signals can be shifted downfield by
+30 ppm!
•  Chelation has erratic
effects dependent on the
ring size, +20 ppm to -20 ppm
 Spectroscopy of 31P

•  31P
NMR is very useful but it is an
empirical tool.
•  Empirical evidence is based on
experience or prior data. Chemical shifts
are very difficult to deduce based on first
principles or theory.
 Spectroscopy of 31P

•  31P
NMR is very useful but it is an
empirical tool.
•  Coordination to the metal usually shifts
ligand signals upfield. But 31P signals
can be shifted downfield by +30 ppm!
•  Chelation has erratic
effects dependent on the
ring size, +20 ppm to -20 ppm
 Character of P(III)
•  What kind of a ligand is PR3?
–  Is it a good donor ?
–  Is it a good σ or good π donor ?
–  Is it a π acceptor ?
•  Look at the complexes formed by PR3
–  Structure
–  Spectroscopy (IR, NMR, etc..)
 Synthesis of M-PR3 complexes
CO CO
L
CO L CO
+ 2 PPh3
OC Mo CO OC Mo CO OC Mo CO
OC L L
OC OC CO

PPh3 = L cis
trans

•  (OC)4M(PX3)2 cis Octahedral

complexes are more stable than
trans isomers.
 Unusual Preference for cis coordination

•  (OC)4M(PX3)2 cis Octahedral

complexes are more stable than
trans isomers.
CO L
L CO
OC Mo CO OC Mo CO
L L
OC CO cis
trans
•  (OC)3M(PX3)3 Octahedral
complexes with fac geometry
geometry are more stable.
CO
L
L CO
OC Mo L OC Mo L
L L
CO CO
mer
fac

CO stretching frequency
is dependant on trans
ligand.
 Traditional explanation
•  PR3 groups π acceptors
–  Lone pair is a donor; Remember 3s and 3p
are valence orbitals; they are filled!
–  3d is empty. (Acceptor strength comes
from 3d orbitals: correct symmetry!)
Traditional explanation

P Mo

z axis

P Mo
x axis

dxz on P and - dxz on Mo

 Traditional explanation

P Mo

z axis

P Mo O
x axis

dxz on P and - dxz on Mo

P Mo

z axis

P Mo O
x axis

dxz on P and - dxz on Mo

 fac ML3(CO)3 Ligand L=PY3
Variation of CO stretching
frequency L
CO
dien 1898 1758 OC Mo L
L
Mecn 1915 1783
CO
Ph 1934 1835
fac
Et 1937 1841

OMe 1977 1888

OEt 1994 1922

CO 2004

Cl 2040 1991

F 2090 2055
ML3(CO)3 Ligand L=PY3
2150 Variation of CO stretching
frequency
2100
Series1 Series2
2050

2000

1950

1900

1850

1800

1750

1700
0 2 4 6 8 10
Dien, MeCN,Ph,ET,OMe,OEt,CO, Cl, F

Electron donating power

 Bonding in phosphines
•  ⇒ 3s 3p orbitals are valence
orbitals

•  d orbitals on P ?
–  3d – higher lying virtual orbitals

•  Controversy 3p – 3d energy
gap is v-large

•  How do you measure energy

levels of empty orbitals ?
 “σ Only or No π” explanation
•  Decrease in νCO is proportional to electron
density on the metal atom.
–  If PY3 is a good donor ligand, then M has greater
electron density,
–  then CO has less stretching frequency.

•  PY3 is a weak σ donor! νCO is HIGHER!

.
P Mo

z axis

P Mo O
x axis

dxz on P and - dxz on Mo

 Ionization Potential
•  Reasons for saying PY3 is a
weak donor.

•  PBu3 8.0 eV
•  PPh3 8.2 eV
•  PF3 13.0 eV

•  So as you increase the IP, the

donor ability will come down.
 Basicity of phosphines
Ligand pKa

(But)3P 11.4

Cy3P 9.7

Et3P 8.69

Me3P 8.65

(Bun)3P 8.43

PPh3 2.43

Ph2(OMe)P 2.69

A bigger list is given in p. 49 (Elias and Gupta)

 Only “σ donation” explanation
•  This explains all the observed results from
IR stretching frequencies. There are no π
effects and PX3 is a weak σ donor!
•  Is there anything else we expect from this
explanation?
•  YES!! Expect:
–  Longer P-M bonds due to poor P to M
bonding.
 “No π bond” theory fails
•  (Ph3P)-Cr-(CO)5 {(PhO)3P}-Cr-(CO)5

•  Expect strong bonds in PPh3 relative to

P(OPh)3
•  P-Cr Cr-C P-Cr Cr-C
•  2.422 1.844 2.309 1.861

•  J.Am.Chem.Soc.
–  1969, 91, 4326
 “No π bond” theory fails
• 
PPh2
2.22 PPh3
2.32
2.24
Rh PPh3
Ph3P
2.17 2.32
F 3C P Pt Cl
2.37
Cl
F 3C
2.37
Cl
 Will the π bond theory fit?
•  When X is electron withdrawing, it causes
the 3d orbital to become lower in energy
(contract). Makes PX3 a good acceptor.

•  M-P will be short in M-PX3 complexes.

•  (Ph3P)-Cr-(CO)5 {(PhO)3P}-Cr-(CO)5

•  2.422 1.844 2.309 1.861

•  J.Am.Chem.Soc. 1969, 91 , 4326

•  Bonding cannot be explained only by
sigma bonds! It is clearly dependent on
“other effects”..
•  Negative hyperconjugation or donation of
Metal’s filled orbitals to σ * orbital of P-X
•  σ * orbitals on P
P-X σ * can accept e- density
•  What is their shape?
 STO-3G
MOs 6-12 Energy (eV)

10.3

7.7

-4.4

-8.9

-16.2
•  Why PR3 groups are π acceptors ?
•  Since P is less electronegative than
H, contribution of P p orbitals to the
σ* orbitals is greater!
•  AsY3 and SbY3 should also be good
as they are less electronegative than
H.
•  Why NR3 groups are not π
acceptors ?
•  N is more electronegative
than H and so bonding orbital
has greater contribution from
N and the σ * has mostly
contribution from H!
 STO-3G
MOs 2-8 for NH3 Energy (eV)

13.0
10.9

-3.9

-11.2

-22.1
•  Secondly, one might notice the energy
level of the NH3 sigma* is higher for NH3
compared to PH3.
•  The lower the energy of the sigma*, the
better it is as a π acceptor.
 STO-3G
MOs 2-8 for NH3 Energy (eV)

13.0
10.9 10.3

7.7

-3.9
-4.4

-8.9
-11.2

-16.2
-22.1
•  Electronegativity difference between A and H in
AH3 is responsible for the greater contributions
of H to the σ* orbitals in P, As and Sb.
 Ligand PY3
2150

2100
Series1 Series2

dien 1898 1758 2050

2000
Mecn 1915 1783
1950

Ph 1934 1835 1900

Et 1937 1841 1850

1800
Ome 1977 1888
1750
Oet 1994 1922
1700
0 2 4 6 8 10

CO 2004
Dien, MeCN,Ph,ET,Ome,Oet,CO, Cl, F
Cl 2040 1991

F 2090 2055 Electron donating power

 Ligand PY3 Mo(CO)6

dien 1898 1758

Mecn 1915 1783

Ph 1934 1835

Et 1937 1841

Ome 1977 1888

Oet 1994 1922

CO 2004

Cl 2040 1991

F 2090 2055
Dien, MeCN,Ph,ET,Ome,Oet,CO, Cl, F
 Explanation of Graph
•  Decrease in CO frequency
happens because, CO competes
against CO in Mo(CO)6 but in
these fac compounds, CO is
competing against a poor π
acceptor.
• 
 Explanation of Graph
•  Trends are reversed. With X=Cl
and X=F,
•  trans CO has greater stretching
frequencies than Mo(CO)6! PCl3
and PF3 are better π acceptors
Tolman’s Electronic Parameter
 Caveats..
•  π effects alone may not be
sufficient, polarization of the
SHARED d orbital also plays
a role!! .
•  Charge induced on the metal
plays a role.
 Better understanding through
controversy / discussion
•  Bonding in phosphines

•  Why are PR3 groups π acceptors and NR3

groups are not ?

•  d orbitals on P ⇒
–  3s 3p orbitals are valence orbitals
•  3d – higher lying virtual orbitals
 Better understanding through
controversy / discussion
•  Controversy 3p – 3d energy gap is v-large

•  ‘MO’ theory of amines & phosphines.

•  σ * orbitals on P – can accept e- density

 Phosphines: Key concepts
•  A versalite π acceptor PR3 –
•  Where are the π bonds in P?
•  π bonding can come from σ* in ligands.
•  Charge effects are important. (intangible)
•  Electronic properties of PR3 can be tuned by
varying R.
•  accepting property of PR3 is maximum when
R is electron withdrawing as in PF3
–  the accepting power is ≥ CO
Phosphorus(III) Ligands

Alternatives to CO
Good Supporting Ligands
ORGANOMETALLIC
CHEMISTRY

M-C
Overview of Ligands
C-Ligands
Non-C Ligands
 Advantages of P(III) Ligands
•  Phosphorus in oxidation
state(III); A pair of electrons
on P can be donated to the
metal.

•  Reaction PX3 with RMgX will

make PR3

•  Can be done stepwise.

 Characterization of P(III)
Ligands
•  X-ray crystallography of PPh3 complexes
is very common.
•  31P NMR spectroscopy is possible &
useful
•  IR spectroscopy is of little use
 Spectroscopy of 31P

•  31P
NMR is very useful but it is an
empirical tool.
•  Coordination to the metal usually shifts
MOST ligand signals upfield.
–  But 31P signals can be shifted downfield by
+30 ppm!
•  Chelation has erratic
effects dependent on the
ring size, +20 ppm to -20 ppm
 Spectroscopy of 31P

•  31P
NMR is very useful but it is an
empirical tool.
•  Empirical evidence is based on
experience or prior data. Chemical shifts
are very difficult to deduce based on first
principles or theory.
 Spectroscopy of 31P

•  31P
NMR is very useful but it is an
empirical tool.
•  Coordination to the metal usually shifts
ligand signals upfield. But 31P signals
can be shifted downfield by +30 ppm!
•  Chelation has erratic
effects dependent on the
ring size, +20 ppm to -20 ppm
 Character of P(III)
•  What kind of a ligand is PR3?
–  Is it a good donor ?
–  Is it a good σ or good π donor ?
–  Is it a π acceptor ?
•  Look at the complexes formed by PR3
–  Structure
–  Spectroscopy (IR, NMR, etc..)
 Synthesis of M-PR3 complexes
CO CO
L
CO L CO
+ 2 PPh3
OC Mo CO OC Mo CO OC Mo CO
OC L L
OC OC CO

PPh3 = L cis
trans

•  (OC)4M(PX3)2 cis Octahedral

complexes are more stable than
trans isomers.
 Unusual Preference for cis coordination

•  (OC)4M(PX3)2 cis Octahedral

complexes are more stable than
trans isomers.
CO L
L CO
OC Mo CO OC Mo CO
L L
OC CO cis
trans
•  (OC)3M(PX3)3 Octahedral
complexes with fac geometry
geometry are more stable.
CO
L
L CO
OC Mo L OC Mo L
L L
CO CO
mer
fac

CO stretching frequency
is dependant on trans
ligand.
 Traditional explanation
•  PR3 groups π acceptors
–  Lone pair is a donor; Remember 3s and 3p
are valence orbitals; they are filled!
–  3d is empty. (Acceptor strength comes
from 3d orbitals: correct symmetry!)
Traditional explanation

P Mo

z axis

P Mo
x axis

dxz on P and - dxz on Mo

 Traditional explanation

P Mo

z axis

P Mo O
x axis

dxz on P and - dxz on Mo

P Mo

z axis

P Mo O
x axis

dxz on P and - dxz on Mo

 fac ML3(CO)3 Ligand L=PY3
Variation of CO stretching
frequency L
CO
dien 1898 1758 OC Mo L
L
Mecn 1915 1783
CO
Ph 1934 1835
fac
Et 1937 1841

OMe 1977 1888

OEt 1994 1922

CO 2004

Cl 2040 1991

F 2090 2055
ML3(CO)3 Ligand L=PY3
2150 Variation of CO stretching
frequency
2100
Series1 Series2
2050

2000

1950

1900

1850

1800

1750

1700
0 2 4 6 8 10
Dien, MeCN,Ph,ET,OMe,OEt,CO, Cl, F

Electron donating power

 Bonding in phosphines
•  ⇒ 3s 3p orbitals are valence
orbitals

•  d orbitals on P ?
–  3d – higher lying virtual orbitals

•  Controversy 3p – 3d energy
gap is v-large

•  How do you measure energy

levels of empty orbitals ?
 “σ Only or No π” explanation
•  Decrease in νCO is proportional to electron
density on the metal atom.
–  If PY3 is a good donor ligand, then M has greater
electron density,
–  then CO has less stretching frequency.

•  PY3 is a weak σ donor! νCO is HIGHER!

.
P Mo

z axis

P Mo O
x axis

dxz on P and - dxz on Mo

 Ionization Potential
•  Reasons for saying PY3 is a
weak donor.

•  PBu3 8.0 eV
•  PPh3 8.2 eV
•  PF3 13.0 eV

•  So as you increase the IP, the

donor ability will come down.
 Basicity of phosphines
Ligand pKa

(But)3P 11.4

Cy3P 9.7

Et3P 8.69

Me3P 8.65

(Bun)3P 8.43

PPh3 2.43

Ph2(OMe)P 2.69

A bigger list is given in p. 49 (Elias and Gupta)

 Only “σ donation” explanation
•  This explains all the observed results from
IR stretching frequencies. There are no π
effects and PX3 is a weak σ donor!
•  Is there anything else we expect from this
explanation?
•  YES!! Expect:
–  Longer P-M bonds due to poor P to M
bonding.
 “No π bond” theory fails
•  (Ph3P)-Cr-(CO)5 {(PhO)3P}-Cr-(CO)5

•  Expect strong bonds in PPh3 relative to

P(OPh)3
•  P-Cr Cr-C P-Cr Cr-C
•  2.422 1.844 2.309 1.861

•  J.Am.Chem.Soc.
–  1969, 91, 4326
 “No π bond” theory fails
• 
PPh2
2.22 PPh3
2.32
2.24
Rh PPh3
Ph3P
2.17 2.32
F 3C P Pt Cl
2.37
Cl
F 3C
2.37
Cl
 Will the π bond theory fit?
•  When X is electron withdrawing, it causes
the 3d orbital to become lower in energy
(contract). Makes PX3 a good acceptor.

•  M-P will be short in M-PX3 complexes.

•  (Ph3P)-Cr-(CO)5 {(PhO)3P}-Cr-(CO)5

•  2.422 1.844 2.309 1.861

•  J.Am.Chem.Soc. 1969, 91 , 4326

•  Bonding cannot be explained only by
sigma bonds! It is clearly dependent on
“other effects”..
•  Negative hyperconjugation or donation of
Metal’s filled orbitals to σ * orbital of P-X
•  σ * orbitals on P
P-X σ * can accept e- density
•  What is their shape?
 STO-3G
MOs 6-12 Energy (eV)

10.3

7.7

-4.4

-8.9

-16.2
•  Why PR3 groups are π acceptors ?
•  Since P is less electronegative than
H, contribution of P p orbitals to the
σ* orbitals is greater!
•  AsY3 and SbY3 should also be good
as they are less electronegative than
H.
•  Why NR3 groups are not π
acceptors ?
•  N is more electronegative
than H and so bonding orbital
has greater contribution from
N and the σ * has mostly
contribution from H!
 STO-3G
MOs 2-8 for NH3 Energy (eV)

13.0
10.9

-3.9

-11.2

-22.1
•  Secondly, one might notice the energy
level of the NH3 sigma* is higher for NH3
compared to PH3.
•  The lower the energy of the sigma*, the
better it is as a π acceptor.
 STO-3G
MOs 2-8 for NH3 Energy (eV)

13.0
10.9 10.3

7.7

-3.9
-4.4

-8.9
-11.2

-16.2
-22.1
•  Electronegativity difference between A and H in
AH3 is responsible for the greater contributions
of H to the σ* orbitals in P, As and Sb.
 Ligand PY3
2150

2100
Series1 Series2

dien 1898 1758 2050

2000
Mecn 1915 1783
1950

Ph 1934 1835 1900

Et 1937 1841 1850

1800
Ome 1977 1888
1750
Oet 1994 1922
1700
0 2 4 6 8 10

CO 2004
Dien, MeCN,Ph,ET,Ome,Oet,CO, Cl, F
Cl 2040 1991

F 2090 2055 Electron donating power

 Ligand PY3 Mo(CO)6

dien 1898 1758

Mecn 1915 1783

Ph 1934 1835

Et 1937 1841

Ome 1977 1888

Oet 1994 1922

CO 2004

Cl 2040 1991

F 2090 2055
Dien, MeCN,Ph,ET,Ome,Oet,CO, Cl, F
 Explanation of Graph
•  Decrease in CO frequency
happens because, CO competes
against CO in Mo(CO)6 but in
these fac compounds, CO is
competing against a poor π
acceptor.
• 
 Explanation of Graph
•  Trends are reversed. With X=Cl
and X=F,
•  trans CO has greater stretching
frequencies than Mo(CO)6! PCl3
and PF3 are better π acceptors
Tolman’s Electronic Parameter
 Caveats..
•  π effects alone may not be
sufficient, polarization of the
SHARED d orbital also plays
a role!! .
•  Charge induced on the metal
plays a role.
 Better understanding through
controversy / discussion
•  Bonding in phosphines

•  Why are PR3 groups π acceptors and NR3

groups are not ?

•  d orbitals on P ⇒
–  3s 3p orbitals are valence orbitals
•  3d – higher lying virtual orbitals
 Better understanding through
controversy / discussion
•  Controversy 3p – 3d energy gap is v-large

•  ‘MO’ theory of amines & phosphines.

•  σ * orbitals on P – can accept e- density

 Phosphines: Key concepts
•  A versalite π acceptor PR3 –
•  Where are the π bonds in P?
•  π bonding can come from σ* in ligands.
•  Charge effects are important. (intangible)
•  Electronic properties of PR3 can be tuned by
varying R.
•  accepting property of PR3 is maximum when
R is electron withdrawing as in PF3
–  the accepting power is ≥ CO
 Alterna(ves+to+CO+

Non+Carbon+Ligands+with+binding+
proper(es+similar+to+CO+
+
Alterna(ves+to+CO+
+ +
+
+
CO+ +++
+ +
CS
+ Change+O+to+S;+++
!
+ !
CSe+ Change+O+to+Se++
+ ++
+
+
Alterna(ves+to+CO+
+ +
+
+
CO+
+++
+
;+ +
CN Change+O+to+N;+And+add+one+more+electron++
+ so+add+an+electron+to+get+CN"!
!
+
CN+R+
;
(CN ++and++H++,+a+proton+does+not+change++
+ electron+count,+it+only+removes+–ve+charge)+
+ +
C(NHR)OR’+ Alcoholysis+product+of+RNC+++
+ +
C(OR)R+ Fischer+Carbene+
+ +
+ +
CR2+ Schrock+carbene+
+ ++
+
+
Alterna(ves+to+CO+
+ +
+
+
CO+ +++
+ +
++
++
+ +What+will+happen+if+we+replace+C+with+other+elements!+
+ ++
+ ++
NO!+ N+has+one+more+electron+than+C:+It+is+s(ll+less+electronega(ve+
+ than+O!+
+
+
Alterna(ves+to+CO+
+ +
+
+
CO+ +Remember+CO+is+a+good+ligand+because+it+has+a++
+ It+has+a+σ++HOMO+on+C+
++ It+has+empty++π*+on+C+
+ It+has+filled+π+on+O+
+ +
+ ++
+ ++
+ ++
+ ++
NO!++ N+has+one+more+electron+than+C:++so+remove+it!+
+ +
+ Since+N+is+less+electronega(ve+than+O,+it+will+behave+as+CO!+
The+difference+between+N+and+O+in+electronega(vity+is+smaller+
and+so+the+good+effects+seen+in+CO+are+likely+to+be+less!+
+
+
++
 ;
NO+/+NO +/+NO ++

•  Lewis+dot+structure+of+NO+is+
instruc(ve+
+++++!.!
++++:N=O:!!!
⋅!⋅
! !!!!!!!! !!
!!
!
 MO+descrip(on+of+NO+
•  Energy+diagram+is+similar+to+the+MO+
descrip(on+of+CO!+

•  Since+NO+has+one+more+electron+
than+CO,+it+is+housed+in+the+π*+
orbital+of+NO.+This+is+the+HOMO!+
–  The+π*+orbital+has+greater+contribu(on+
from+N+and+so+the+electron+is+mostly+
localized+on+N!+
•  9.3+eV+is+the+IP+of+NO+
 MO+descrip(on+of+NO ++

•  It+is+similar+to+the+MO+descrip(on+of+CO!+

•  Since+NO++has+a+HOMO+on+N,++
•  π*+orbital+of+NO+is+the+LUMO.+More+
contribu(on+from+N+and+so+when+bound+to+
the+metal,+the+interac(ons+of+M;NO+are+
similar+to++interac(ons+of+M;CO!++

•  The+π*+orbital+has+greater+contribu(on+from+
N+and+so+the+back+dona(on+of+electrons+
from+metal+goes+into+N!+

•  [M=N=O]+++is++the+structure+to+expect.++
•  Neutral+NO++
–  N;O+distance+is+1.15++Å+
– νNO+is+1904+cm;1+

•  NO+++++isoelectronic+to+CO!+
– νNO+is+2376+cm;1+
–  N;O+distance+is+1.072++Å

•  OX.+Poten(al+of+NO++is+23+eV++
–  whereas+CO++is+ionized+at+15+eV+
 ++charge++2+e;+donor+ligand!+

•  [V(CO)5NO]+is+a+neutral+complex.+It+is+diamagne(c+

•  If+CO+is+a+neutral+ligand,+5X2+electrons++ +=+10+
•  V+is+a+3d3++4s2+system+so+5+electrons ++++ +=++5+
•  NO+++is+a+2+electron+ligand+ + ++++ + +=++2+
•  Since+the+complex+is+neutral,+we+must++
++++add+an+electron+to+make+it+neutral+++++++ + +=+1++
_________________________++++++++++++++++++++________+
•  Total+no.+of+electrons+ + ++++ + +=+18+
 NO +Ligand+(CO+like+bonding)+
+

•  So+there+are+two+ways+to+count+electrons+
•  IONIC+METHOD!++
–  NO++as+a+2+electron+ligand.++
–  Include+the+++charge!+
•  NEUTRAL+METHOD+
–  NO+is+taken+as+a+neutral+ligand+that++++
–  gives+3+electrons+to+the+system!+
 Cr(NO)4+
•  Consider+the+following+reac(on!+
•  Cr(CO)6+++NO+(g)+++;;;;;;>+++Cr(NO)4+++++6+CO+
•  νNO+is+1721+cm;1+
•  No(ce+how+6+CO+ligands+giving+12+
electrons+are+replaced+by+4+NO+groups.+

•  Neutral+method:+each+NO+gives+3+
electrons+and+so+the+ligands+give+4X3+=+
12+electrons+

•  +Cr+gives+6+e+making+a+total+of+18+++++++++++++++
 IONIC+method+
•  Cr(CO)6+++NO(g)+++;;;;;;>+++Cr(NO)4+++6+CO+
•  4+NO++ligands+require+4–+charges+on+Cr;++
•  So+Cr+is+;4+oxida(on+state.++Becomes+a+d10+
system.+++Complex+looks+like+Ni(CO)4+

From νNO++2376 cm-1

the stretching frequency
has decreased to ν 1721 NO+

cm;1+
+
 Co(NO)3+
•  Consider+the+following+reac(on!+
•  Co2(CO)8+++NO+(g)+++;;;;;;>+++Co(NO)3+++++8+CO+
•  νNO+is++1860+and+1795+cm;1++

•  Neutral+method++
•  each+NO+gives+3+electrons+and+so+
the+ligands+give+3X3+=+9+electrons++
•  Co+gives+9++electrons+
•  Total+18+v.e+complex.+
 Co(NO)3+
•  Co(NO)3++++3NO++++Co3;+++
•  Ionic+method++
–  each+NO++gives+2+electrons+and+the+ligands+
give+3X2+electrons+++
–  Co+gives+9e+and+to+compensate+for+the+
charge+we+add+3+e++++
•  Because of the –ve charge “back
bonding” is more
•  νNO+is++1860+and+1795+cm;1+
 Prepara(on+using+Nitronium+ion+

IONIC!METHOD! NEUTRAL!METHOD!
NO++ 2+ NO+ 3+
Cp;+ 6+ Cp+ 5+
CO+x+2+ 4+ CO+x+2+ 4+
Re+++ 6+ Re+ 7+
Charge+ ;1+
Total+ 18+ Total+ 18+
 Prepara(on+using+the+nitrite+ion+
•  Na+Co(CO)4+++NaNO2+;;;;;;>+Co(CO)3(NO)+++H2O+
++++++HOAc+++++++++++ + + +CO+++2+NaOAc+
+
+
 (C5H5)Mo(NO)(CO)C3H5Re(CO)5+

(µ2;σ1,+η+2;Allyl);hexacarbonyl;(η5;cyclopentadienyl);nitrosyl;molybdenum;rhenium+
(C5H5)Cr(NO)2(ONO)+
 [Ru2Cl8(NO)2]2;+
bis(Methyltriphenylphosphonium)+bis((µ2;chloro);trichloro;nitrosyl;
ruthenium)+dichloromethane+solvate+
 More+similarity+to+CO!+
•  NO+Bridges+two+metal+centres,+just+like+CO!++
Bridging+nitrosyls+
 Bridging+nitrosyls+

(µ2;Carbonyl);(µ2;nitrosyl)+
;bis((η5;pentamethyl;cyclopentadienyl);
rhodium)+hexafluorophosphate+
 ;
NO+/+NO +/+NO ++

•  Let+us+go+back+to+the+Lewis+dot+
structure+of+NO+
+++++!.!
++++:N=O:!!!
⋅!⋅
! !!!!!!!! !!
This!is!likely!to!be!a!1!electron!
ligand,!as!it!has!1e!more!than!
CO!and!that!is!localized!on!N!!
!
 Neutral+NO+is+a+1+electron+ligand!+
•  MO+suggests+that+the+N+will+be+bonded+to+the+
metal+by+sharing+one+electron+with+the+metal.+

•  It+also+suggests+that+NO+can+s(ll+accept+
electrons+into+the+π*+orbital+which+is+
perpendicular+to+this+orbital.++
•  MO+suggests+that+the+N+will+be+bonded+to+the+
metal+by+sharing+one+electron+with+the+metal.+

•  Lewis+dot+descrip(on+suggests+that+the+metal+
gives+one+electron,+and+NO+gives+one+electron+
so+that+a+covalent+bond+is+formed+
Bent+NO+
Bent+and+linear+complexes!+
 Bent+and+Bridging+nitrosyls+
M;N+bond+is+longer+
in+the+bent+ligand.+
+
Oxida(on+state+of+the+
ligand+
NO+is+NO"!!neg.+charge+
+
Frequency+is+lower++as+
there+are+two+
electrons+in+the+
an(bonding++orbital+
1620;1720+cm;1++
!

bis(Tetraethylammonium)+
+µ;chloro;pentachloro;µ;nitrosyl+nitrosyldipla(nate(ii)++
+
Alterna(ves+to+CO+
+ +
+
+
CO+ +++
+ +
++
++
+ ++
+ ++
+ ++
NO!++ N+has+one+more+electron+than+C:++so+remove+it!+
+ +
BF! Subtract+one+electron,+++add+one+electron!+
+ +
BO
;+ +
+ +
BOR+ Recent+paper+++{Chem.+++Eur.Jnl.1998,++++p.210}+
Alterna(ves+to+the+CO+Ligand:+Coordina(on+of+
the+Isolobal+Analogues++BF,+
BNH2+,++BN(CH3)2+,+and++BOR+in+Mono;+and+
Binuclear+First;Row+Transi(on+
Metal+Complexes+
+
Andreas+W.+Ehlers,+Evert+Jan+Baerends,*+F.+
Mashias+Bickelhaupt,+and+Udo+Radius+
+
Chem.+Eur.+J.+1998,+4,+210+
+
+
 BO
"!
NN+ CO+ BF+ BNH2+

eV+

+6+

0++

;2+

;4+
99+%+
90+%+ 0.44+
;+8+ 0.46+
98+%+
;10+ 90+%+ 0.48+
0.42+
50+%+
0.27+
The+contribu(on+of+the+atom+bonded+to+the+metal+is+shown+in+%+
Below+that+is+the+overlap+with++Fe(CO)4+
 !HypotheIcal!binding!energy!+
E+(eV)++

NN+ CO+ BF+ SiO+

0+

;5+

;10+

77++++++ 177++++++ 280++++++ 157++++++

LFe(CO)4+ Fe(CO)4+++++L++ΔH+diss+
 !Dinitrogen!+
•  !Dinitrogen!AcIvaIon!by!Titanium!Sandwich!
Complexes+
Tamara+E.+Hanna+,+Emil+Lobkovsky+,+and+Paul+J.+
Chirik+*+
J.#Am.#Chem.#Soc.,+2004,+126+(45),+pp+14688–14689+

•  IP+is+15.8+eV++
•  It+is+easier+to+ionize+CO.+It+costs+only+15+eV!+
+
Ti(II)N2+complex+
•  Group!4!TransiIon!Metal!Sandwich!
Complexes:!SIll!Fresh!aRer!Almost!60!Years!
Paul+J.+Chirik+
Organometallics#2010+29+(7),+1500;1517+
Coordina(on+and+Ac(va(on+of+the+BF+Molecule**+
Dragoslav+Vidovic+and+Simon+Aldridge*+ Angew.+Chem.+Int.+Ed.+2009,+48,+3669+–3672+

Ru
OC F
B
OC
F
Metal Alkyls
Preparative methods
 METAL ALKYLS
•  Group Trends

• Electropositive character of the

•  Be metal.
•  Mg • Size of the metal
•  Ca
•  Sr • Electronegativity changes in the
opposite direction.
•  Ba

• Reactivity of R2M
 METAL ALKYLS
•  Remember that R2M is still not saturated.
•  R gives 1 electron, and so the ns orbital and
one np are filled.
•  Two np orbitals are vacant.
•  Usually this means you have some other
species coordinated to the metal in alkyl-
metal complexes.
–  Solvent, ligand etc… Determine the reactivity
–  Better coordination and stabilization… poor
reactivity
 METAL ALKYLS
•  Mg + RX RMgX(Et2O)n

•  Unsolvated Grignards are difficult to make.

•  RX becomes more reactive with increasing
leaving group ability
–  F<<Cl<Br<I
•  F is almost impossible to break (C-F vs C-Cl)
 METAL ALKYLS
•  Problems with Grignard reagents
–  Preparation needs surface activation
–  Solvent, presence of other RM can affect
reactivity
–  X group affects reactivity
 METAL ALKYLS
•  Problems with Grignard reagents
–  Preparation needs surface activation
–  Solvent, presence of other RM can affect
reactivity
–  X group affects reactivity
 METAL ALKYLS
•  Schlenk Equilibrium
–  R2M +MX2 ! 2 RMX
–  Makes solutions of R2M containing metal salts
different from solution of R2M without MX!
•  Radical type reactions ……
 METAL ALKYLS
Radical type reactions
RX + Mg RMgX

RX-. + Mg+. R. + MgX.

 METAL ALKYLS
•  Radical character from reactivity

.
•  R can be detected by trapping
experiments
O.

H3C N CH3

H3C CH3

TEMPO
 METAL ALKYLS
•  Reike Magnesium

•  Extremely reactive magnesium

generated in situ from MgCl2 and K/
THF reflux temperature.

•  MgCl2 + 2K “Mg” + 2KCl

•  “Mg” Black powder , pyrophoric

 METAL ALKYLS

Reike Magnesium could even activate

C-O bonds!!

O "Mg" O
Mg

"#
METAL ALKYLS
"Mg "
Mg .2THF

(THF)3

Mg
"Mg"
 METAL ALKYLS

•  Mg + H2 MgH2

•  Hydrogen Storage
•  Catalyst for the above reaction
• 
(THF)3

Mg
Very complex structures
THF
THF
Mg
Mg

Mg Mg

THF
THF
Very complex structures

O
H3C
O O

Mg
O O
CH3

O O
Very complex structures

CH 2.30

2+
Mg
1.39
CH
 THF
THF
Mg
Mg

Mg Mg

THF
THF

How do you explain the

Bonding in these bridges
 M
M M
M

1C (sp2 hybrid) and 2 metal

orbitals (suitably hybridized)
M
M
Only 2 electrons in C!
 METAL ALKYLS

•  Aluminum (very reactive)

•  Direct reaction between

Al + RX possible
 METAL ALKYLS
•  Mercury is predominantly covalent

•  Surprisingly, the two bond energies are very

different

HgMe2 HgMe + Me 214 kJ/Mol

HgMe Hg + Me 29 kJ/Mol

•  So it is easy to dissociate the Me or R as R .

 METAL ALKYLS
Preparation

•  Hg.Na (sodium amalgam) reacts readily with a

variety of RX to give R2Hg + NaX

•  PhH + Hg(OAc)2 ===> PhHgOAc + HOAc

–  (Electrophilic substitution of aromatic ring)
Transition metal alkyl complexes
 Transition metal alkyl
complexes
•  Preparation follows TmXn + PhCH2MgCl
–  ZrCl4 + BenzylMgCl >>> (Benzyl)4Zr

•  TiCl4 + Al2Me6 >>>>> MeTiCl3

•  Corresponding ethyl compound is not

stable!
 Initial thought:
Tm-R bond is weak
•  Cp2TiPh2 M-C bond energy is 330 kJ/mol

•  Ti(CH2Ph)4 Average M-C is 260 kJ/mol

•  Zr R4 Average M-C is 310 kJ/mol

•  WMe6 Average is 160 kJ/mol (-110)

 Tm-C are not weak…they
are reactive
•  Instability due to kinetic factors
and not thermodynamic factors.

•  Beta hydride elimination gives

alkene / hydride complexes
 Transition metal alkyls

H
H
H2 H 2
Ln CH3
Tm Ln C C
Tm
H

beta agostic bond

alpha agostic bond
 Detection
•  Unusual bond angles (X-ray)
–  Affects coupling constants in NMR

•  short distances (X-ray and NMR)

•  Not detected in IR
 What makes them have
agostic interactions?

•  Deficiency in the electron

count around the metal.

•  C-H bonds as electron

donors
How to avoid agostic
interactions?

•  Only one way! Avoid

C-H bonds in the beta
positon
•  Bridge head alkyls
–  CH2CF3
–  CH2CMe3
–  CH2C6H5
–  CH3
 Summary
•  Metal Alkyls:
•  Different ways of making them.
•  Schlenk equilibria.
•  Metal alkyls and how they generate anions and radicals.
•  Bond strength variation in transition metal alkyls.
•  Kinetic instability of metal alkyls.
•  Agostic interactions in metal alkyls.
•  Electron deficiency in metal alkyls. 3C – 2e and 3C –
4C bonding.
 Role of OM in Organic Synthesis
Me Me Me
Me

a
rac-32 b OMgCl c OH d OH
Ti OH
Zr Cu 99%
Et Et Et
40%
MgCl NHTs NH2
32 33 34 30

MgCI
h
e f g
O Ru
OH OMgCl Ni OH
Zr Ti 65% Et CO2H
Et Et 72% Et
i 60%
37 38 31
35 36 j 90%
Me Me
Me

OTBS
OTBS K
OTBS
I
m Mo O
Pd O Et Et
27 O Et Et
80% Et Et 60%
75% HN
HN
HN
39
40
41
Reaction
Subtype! Comment!
type!
Substitution reactions!

nucleophilic
with SN1, SN2 and SNi reaction
aliphatic
mechanisms!
substitution!
aromatic !
Addition reactions! halogenation, hydrohalogenation !
electrophilic ! Inser&on(of(a(neutral(group(
nucleophilic !
radical !
Elimination reaction! !Reverse(of(the(addi&on,(extrusion(
Organic redox reactions! !Addi%on!of!electrons,!H,!!!
Removal!of!electrons,!O,!!!
Rearrangement reactions!
pericyclic
!σ(bonds(or((π(bonds(are(rearranged.!!
reactions!
 Is there a rational way to understand
all organic reactions?

•  ~YES! We can use the Functional Group

approach.
o Reagent A converts FG1 to FG2 in molecule 1
CH3CH2-CH=CH-CO-CH3 to CH3CH2CH2CH2-CHOH-CH3
o  Same reagent A used in molecule 1 will
convert FG1 to FG2 in molecule 2 also.
 Is there a rational way to understand all
organometallic reactions?
•  Can we use a Functional Group approach?
o Can expect similar reactivity for metals of the
same group?
o HRhCl(PPh3)2 and HCoCl(PPh3)2
o Can we substitute ligands with similar electron
counts and achieve similar / better results?
o [CpCo(CO) 2] / [CpCo(PMe3)2]

o  Answer to the 2nd question: maybe yes!

o Answer to the 1st one: NO!..
 Multiple Insertion Reactions
•  Acetylenes >>>> Arene, cyclobutadiene,
polyacetylenes,
•  Best Catalyst for arene synthesis from alkynes:
CpCo(CO)2
•  Next best complex is not Rh / Ir analog!
•  It is PdCl2, PdCl2 can also “stitch” acetylenes!
How do we find out the many small steps in
these multistep reactions?

! Are there some fundamental or key steps in these

reactions? Acetylene >> Arene?

! Acetylene > cyclobutadiene >> Arene ?

! How does one figure out which of these steps are

really occurring?

!  MORE IMPORTANTLY

! Which steps are not involved ?

Mechanisms of Organotransition Metal Reactions
Classification of OM Reactions
M - C

A. Rearrangements, Isomerizations

M - L M - L'

B. Ligand Insertion Reactions

X

M L + X M X L

C. Oxidative Addition Reductive Elimination

Mn+ + L M(n+x)+ L

D. Reactivity changes on the Ligand

M L + Y M L' + X
Mechanisms of Organotransition Metal Reactions
Classification of O-TM Reactions
M - C

A. Rearrangements, Isomerizations

M - L M - L'

B. Ligand Insertion Reactions

X

M L + X M X L

C. Oxidative Addition Reductive Elimination

Mn+ + L M(n+x)+ L

D. Reactivity changes on the Ligand

M L + Y M L' + X
Mechanisms of Organotransition Metal Reactions
Classification of OTM Reactions
M - C

A. Rearrangements, Isomerizations

M - L M - L'

B. Ligand Insertion Reactions

X

M L + X M X L

C. Oxidative Addition Reductive Elimination

Mn+ + L M(n+x)+ L

D. Reactivity changes on the Ligand

M L + Y M L' + X
Mechanisms of Organotransition Metal Reactions

Classification
M - C
of OM Reactions
A. Rearrangements, Isomerizations

M - L M - L'

B. Ligand Insertion Reactions

X

M L + X M X L

C. Oxidative Addition Reductive Elimination

Mn+ + L M(n+x)+ L

D. Reactivity changes on the Ligand

M L + Y M L' + X
R O
Mg X + CO2 R
O
Mg X

O
CH3OH + CO H3C
HO

Ph4As+ [Rh(CO)2I2]- HI , 800 C / 3 atm of CO

Monsanto's acetic acid process

annual production 106 tons.
R O
Mg X + CO2 R
O
Mg X

OXO synthesis
Co / Rh
H3C CH2
H3C O
+ H2 + CO

7 million tonnes of aldehydes

Essential catalyst HCo(CO)4
 H

Co / Rh
CH2
O
+ H2 + CO
OH
HO
H
H
H
Raney Nickel
H
O
O
H2
OH
OH
O Rh catalyst O
+ CO
O
O O
 Main Group Insertion Reactions
•  Polarity is very important, both fragments
are charged.

•  In transition metal chemistry, we have one

neutral ligand and one “charged” species.
What are the steps involved
 Mn2(CO)10 + Na/Hg NaMn(CO)5

H3C
OC CO
NaMn(CO)5 + MeI Mn
OC CO
CO
Calderazzo
O CH3

H3C
OC CO OC CO
+ CO Mn
Mn
CO OC CO
OC
CO OC
 Mn group insertion reactions
O CH3

H3C
OC CO OC CO
+ CO Mn
Mn
CO OC CO
OC
CO OC

Calderazzo 13CO = CO
O CH3

H3C
OC CO OC CO
+ CO
Mn Mn
CO OC CO
OC
CO OC
 O CH3

H3C
OC CO + CO OC CO Expected product
Mn Mn if it was direct
CO OC CO insertion!
OC
CO OC
 O CH3 CH3
O
H3C
OC CO OC CO + CO OC CO
Mn Mn Mn
OC CO OC OC CO
CO OC OC

Expected product if
entering CO is filling a
vacant coordination site
 O CH3
Entering CO is
H3C
OC CO OC CO filling a vacant
+ CO coordination
Mn Mn
CO OC CO site
OC
CO OC

Calderazzo Direct insertion product

not formed!

O CH3

H3C
OC CO OC CO
+ CO
Mn Mn
CO OC CO
OC
CO OC
 Migratory Insertion with isotopically labelled C
-
Mn2(CO)10 reduce to get Mn(CO)5 + CH3I
Me O
Me
CO OC CO
OC
Mn + 13 CO Mn
13

OC CO OC CO
CO CO

1. Entering CO is merely filling a vacant site.

13
CO 2. It is under kinetic control.

13 O Expected here if it
C was direct insertion.
OC CO
Mn
OC CO
C
O
 13 13
Me O CO
13 O OC CO OC Me
Me C + Na Mn(CO)5 Mn Mn
Cl CO
CO OC
OC CO
CO
Reverse of the previous reaction !

3. Shows that the reacting CO and Me should be cis !

 Me O CO
OC Me CO
CO Mn
Mn 13
OC
13
CO OC CO trans
CO CO
Direct
elimination CO
OC Me
Me Mn
13
OC CO cis
OC CO CO
Mn
13
trans : cis : unlabelled
OC CO CO
CO
1 : 2 : 1 OC CO
Mn
OC Me
CO unlabelled

4. Methyl migrates to a vacant cis site.

Isotopic labelling

I. R.
Migration Produces Coordinatively
Unsaturated Complexes!
Migration through coordinatively
Saturated Complexes!
 Migratory Aptitudes
•  Alkyl > benzyl > allyl > aryl, vinyl >

•  Vinyl > propargyl

•  Groups that don’t usually migrate

–  H, CF3-, RCO-
 STEREOCHEMISTRY OF
MIGRATING CARBON
•  Methyl (anionic ligand / 1 electron donor)
migrates to a cis vacant site.
•  Is it a free “methyl radical” ??
•  Does it undergo inversion? As if it is an SN2
process?
•  Or does it come out like an alkyl cation??
•  One neutral ligand (2 electron donor) M-CO
+ one anionic ligand (1 electron) M-R
•  Anionic ligand migrates from the metal to
the neutral ligand, making the neutral (2
electron donor) ligand anionic (one electron
donor) M-CO-R
•  3 e ligand system " 1 electron ligand!
 Effect of migration
BEFORE AFTER
•  M-R + M-CO •  M-(CO)R
•  2 coordination sites •  One cis coordination site
occupied free
•  Neutral method •  Neutral method
–  3 electrons ; R and CO –  1 electron RCO
•  Ionic method •  Ionic method
–  M+ , R-; CO : 4 electrons –  M+, RCO- 2 electrons
 Plausible combinations for
insertion reactions!
NEUTRAL LIGANDS Anionic Ligands
•  Olefin •  Hydrogen
•  CO •  Alkyl
•  Acetylene •  Aryl
•  NO ? •  Halogen, Chloro
•  Phosphine •  Vinyl