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CHM102A GeneralChemistry

2014 2015
20142015
Part2:InorganicandOrganicChemistry
P
t2 I
i
dO
i Ch i t
G.Anantharaman
garaman@iitk.ac.in

Importantannouncements
Lectures: Feb.
Feb 24,
24 2015 - Apr.
Apr 17,
17 2015
Tutorial: Mar. 9, 2015 - Apr. 13, 2015 (every Monday)
Please note March 14, 2015 is a working day with Monday
class schedule. But there will be no tutorial for Section A
and B, instead a lecture for section A will be there between
9 00 - 9:50
9:00
9 50 h
hrs iin L7
L7.
Quiz (30 Marks): Mar. 27, 2015; 18:30 - 19:00 hrs (venue will
be announced later))
End Sem exam (120 Marks): 2 hrs (time and date will be
announced later by DOAA)
Iwillsendhomeassignmentsandyoucandiscusstheanswersinthe
tutorial

Section A

Section B

Lecture days,

Wednesday, Friday

Tuesday:16:00-16:50 hrs

times

9:00 - 9:50 hrs

Wednesday: 14:00-14:50 hrs

Venue

L7

L7

Section A
Tutorial day

Monday

Ti
Time

9 00 - 9:50
9:00
9 50 hrs
h

Section

Venue

A1

L5

A2

L6

A3

L14

A4

L15

Tutors
Physical
Dr. Nisanth Nair,
M S
Mr.
Sarvesh
hK
K. P
Pandey
d
Dr. D.L.V.K. Prasad
Mr. Soumyadeb Dey
Dr. M. Chandra
Ms. Shalini Awasthi
Dr. K. Srihari
Mr. Chandan K. Das

Inorganic/Organic
Dr. S. K. Kundu
D M
Dr.
M. K
K. Gh
Ghoraii
Dr. A. K. Patra
Dr. D. H. Dethe
Dr. S. Basker
Dr. J. N. Moorthy
Dr. R. Angamuthu
Dr. A. Singh

Section B
Tutorial day

Monday

Time

14:00 - 14:50 hrs

Section

Venue

B1

L5

B2

L6

B3

L11

B4

L12

Tutors
Physical
Dr. S. R. Gadre
Mr. Gopal K. Dixit
Dr. T. G. Gopakumar
Ms Paramita Ghosh
Ms.
Dr. D. Goswami
Ms. Puspal Mukherjee
Dr. N. S. Gajpiye/
Dr. S. Manogaran
Mr. K. Sooraj

Inorganic/Organic
Dr. S. P. Rath
Dr. M. L. N. Rao
Dr. J. K. Bera
Dr R.
Dr.
R Gurunath
Dr. P. K. Bharadwaj
Dr. Y. D. Vankar
Mr. I. A. Bhat
Dr. R. Ramapanicker

Contents
Inorganic Chemistry
Crystal Field Theory: Structure and applications of Coordination
Complexes
Oxidative Addition
Addition, Reductive Elimination,
Elimination Insertion Reactions
Hydrogenation, Hydroformylation, Process and Ziegler-Natta
Polymerization
Organic Chemistry
Conformational Analysis of Alkanes and Cycloalkanes
Chirality
Substitution and Elimination Reactions
Books
Inorganic Chemistry by Shriver and Atkins
Inorganic
i Chemistry:
h i
Principles
i i l off Structure andd Reactivity
i i by
b
J E Huheey, E A Keiter and R L Keiter
O ga c Chemistry
Organic
C e st y by J C
Clayden,
ayde , N G
Greeves,
eeves, S Wa
Warren
e
Fundamentals of Organic Chemistry by T W G Solomons
5

Youwillcomeacross.

Natta

Ziegler
1955
~1890

~1920
2015

vanVleck

1927

Bethe
1930

SirGeoffreyWilkinson
1965

100yearsafterNobelprizethejourneycontinues.

N.P.E. Barry,P.J.SadlerPureandAppliedChemistry,2014,Volume86,Pages18971910

Cyclicpolyethersandtheircomplexeswithmetalsaltsandcircularhelicate
O
O

18crown6potassium
O

O
O

Selective cation recognition


Host-Guest
Host
Guest chemistry
JeanMarieLehn(Nobelprizein1987withD.J.CramandC.J.Pedersen)

ThesimplereactionofatrisbpyligandstrandwithFeCl2 leadsto
theselfassemblyoftheuniquecation1,whichconsistsofa
II ionsina
torusformedbyfiveligandswrappedaroundfiveFe
y
g
pp
doublehelicalfashionandclosedaroundacentralchlorideion.
Thisstructure,afivefoldcircularhelicate,isahelicateanalogue
ofcircularDNA.

C.J.Pedersen,J.Am.Chem.Soc.,1967,89(26),pp70177036
8
AngewandteChemieInternationalEditioninEnglish,year1996, Volume35,pages18381840.

Molecularmachinesandnanotechnology

In this example of a molecular machine we are able to switch between two molecular states (shapes) in a
controlled manner as part of a repetitious mechanical cycle. An azobenzene molecule can exist in two forms
((left: trans with the bulkyy ggroups
p on opposite
pp
sides of the double bond, and right:
g cis with the bulkyy ggroups
p on
the same side). The bulky groups can be moved closer together or further apart by switching between the cis
and trans forms. This switching can be performed by using light of two different colours, one to go from cis to
trans, the other to reverse the process.

Rotary motion around a molecular


axis of a Metallacarborane which
has been controlled by simple
electron transfer processes and by
photoexcitation.

W.R.BrowneandB.L.FeringaNatureNanotechnology2006,1,25 35.
M.F.Hawthrone,Science,2004,303,18491851

Lightdrivenunidirectionalrotarymotorsinaction

a, Principle of cistrans isomerization around a double bond connecting two groups (R). Light absorption induces a rotary
motion around the double bond,
bond which results in a change in the relative position of the two R groups.
groups b,
b Examples of
first and secondgeneration rotary motors that operate by photochemical cistrans isomerization (Meax and Meeq
indicate axial and equatorial orientations of the methyl groups, respectively). c, Secondgeneration rotary motor
immobilized on a gold surface. The first photochemical transtocis isomerization forces the molecule into a highly
strained cisgeometry. Rotary motion continues in the same direction as the consequence of a thermal helix inversion that
results in a release of the strain in the molecule. Subsequent irradiation induces a cistotrans isomerization, which is
followed by a second thermal helix inversion, again with release of conformational strain, to provide the initial state.
10

W.R.BrowneandB.L.FeringaNatureNanotechnology2006,1,25 35.

Transienthemiaminaltrappedinaporousnetwork

Kawamichi,T.,Haneda,T.,Kawano,M.andFujita,M.,Nature 2009, 461, 633

11

Linkers Make a Difference!


IRMOF (isoreticular metal organic frameworks)

Zn4O
Yaghi et al. Science 2003, 295, 469.

12

HybridMetalOrganicFrameworks(MOFs):UpcomingMaterialsforGas
Adsorption/Storage/Sieving

MOFsareframeworkstructuresconsistsofmadeofMetalsandorganic
ligands asnodesandlinkers
TheyhaveapotentialapplicationsinGas/liquidsorption,luminescence,
They have a potential applications in Gas/liquid sorption luminescence
magnetismandcatalysis
Recentlythefocusisgiventodevelopfunctionalcoordinationpolymers
VeryrecentlytheBASFfurthertestedthe
l h
f h
d h
nanocubes ofMOFsasmaterialstoincreasefuel
fuelstoragecapacityinNaturalGasVehicles

The major efforts are going on to develop porous materials with high capability
of storing gaseous molecules such as H2, O2, CO2, and other obnoxious gas
emission from vehicles and transform to usable materials
The key is the modulation of the final structure using appropriate choices of
connectivity in metal and organic ligands
BASF: https://www.youtube.com/watch?v=nSP-VDwKz5o&list=PLvd4K_EStw4iqKi6xo6RkGV9-cbULkceg&index=19
13
BASF: BadischeAnilin undSodaFabrik

Polymers and Conjugated Compounds

carotene

PolyvinylChloride(PVC)
Polystyrene

14

Gum base
Whatt is
Wh
i gum made
d off today?
t d ?
Gum base gives gum that bounceback texture that makes it fun to chew. Each company
keeps their special recipe for gum base a secret, but there is something we can tell
yyou... All ggum bases are made of three kinds of ingredients
g
which ggive ggum its special
p
properties:
Resin the main part you chew
Wax softens the gum
Elastomer adds flexibility

Gumbaseoftencontainspolyethylene(pah
leeethleen),alongmoleculethat'salsoused
tomakeplasticbottlesandplasticbags.

KarlZiegler

GiulioNatta

TheNobelPrizeinChemistry1963
15

http://www.acs.org/content/acs/en/education/whatischemistry/adventuresinchemistry/secretsciencestuff/gum.html

Metallodrugs
Amongthenaturalsciences,medicinalinorganicchemistryisstillconsidereda
rather young discipline by many, but this is contrary to the historically proven
ratheryoungdisciplinebymany,butthisiscontrarytothehistoricallyproven
useofmetalsinpharmaceuticalpotions,whichtracesbacktotheancient
civilizationsofMesopotamia,Egypt,India,andChina
Ehrlich ssalvarsaniswidelyregardedasthe
Ehrlichs
salvarsan is widely regarded as the
birthofmodernchemotherapy

O
O

H3N
Pt
H3N

O
O

Carboplatin (Ovarian Cancer)

contrastagentscontaining
contrast
agents containing
radioactivemetalisotopes

Technetium (99mTc) sestamibi


Single photon emission computed tomography

16

FromChemicalengineer@IITKtotumorpathophysiology

NH

N
N

N
N

HO
Cl

Losartan

RakeshK.JainistheAndrewWerkCookProfessorof
Rakesh
K. Jain is the Andrew Werk Cook Professor of
TumorBiologyatMassachusettsGeneralHospitalin
theHarvardMedicalSchool.Dr.Jainprimarily
researchestumorpathophysiology

17

18

Periodic table

Noneedtomemorizeyouwillbeprovidedintheexam
19

Earlier reaction by Werner and elucidation of octahedral structure


Different cobalt(III) complexes were isolated upon the addition of aqueous ammonia
to aqueous solution of CoCl2
The +3 oxidation state.
A fourth complex can be made by slightly different techniques.
All the four complexes have different colors and different empirical formulas
confirmed through silver nitrate test and conductivityofionsinsolution
conductivity of ions in solution
for example treatment of silvernitrate solution to CoCl3 6NH3gavethreeequiv.ofchlorideions;

Compound
CoCl3 6NH3
CoCl3 5NH3 H2O
CoCl3 4NH3
CoCl3 4NH3

Color
No.andequivofAgCl ppt.
orangeyellow
3
red
2
purple
1
green
1

20

ProposedStructuresfor6CoordinateCobalt(III)complex

21

Ligands
Neutral molecules or ions having a lone electron pair that can be used to form a bond to
a metal ion.

M
Monodentate
d
ligand
li
d one bond
b d to a metall ion
i
N

O
H

H
water
Cl-

chloride

H
ammonia

carbon monoxide

C
N
cyanide

S
C
N
thiocyanate

Bi and polydentate ligand Two or more bonds to a metal ion

22

Most Common Geometries

23

Isomerism
On finding compounds with different properties follow the chart below

Let us take an example[Co(NH3)5(NO2)]Cl2


Two complexes differs by distinct colors

24

Linkage Isomerism
Occurs with ambidentate ligands. These ligands are capable of coordinating in more
than one way. The best known cases involve the monodentate ligands SCN / NCS and
NO2 / ONO.

[Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2

25

Ionization Isomerism
Theyy form different ions in solution.
[Cr(NH3)5SO4]Br and [Cr(NH3)5Br]SO4
[PtBr(NH3)3]NO2 and [Pt(NO2)(NH3)3]Br

Coordination Isomerism
Found in compounds in which both cations and anions are complexes, through the
exchange of some ligands from the cationic part to the anionic part
[Co(NH3)6] [Cr(C2O4)3] and [Co(C2O4)3] [Cr(NH3)6]
[Zn (NH3)4] [CuCl4] and [ZnCl4] [Cu(NH3)4]

Hydrate Isomerism
Through the replacement of coordinated groups by water molecules
[CrCl2(H2O)4]Cl2H2O (bright-green)
[[CrCl(H
( 2O))5]]Cl2H2O (g
(grey-green)
yg
)
[Cr(H2O)6]Cl3 (violet)
26

Geometrical Isomerism
Geometrical isomerism is ppossible with square
q
pplanar and octahedral complexes
p
but not
with tetrahedral complexes.
Square
q
planar Complexes
p
p
Ma2b2 2 isomers are possible (cis and trans)
NH3
Cl

Pt

Cl
Cl

NH3

trans

Cl

Pt

NH3

NH3

cis

Mabcd 3 isomers are possible

27

Geometrical Isomerism
Octahedral Complexes
Ma4b2 2 isomers are possible (cis and trans)
NH3

Cl
H3N
H3N

H3N
H3N

NH3
NH3

Co

Co

NH3
Cl

Cl
cis

Cl
trans

M 3b3 2 isomers
Ma
i
are possible
ibl (fac
(f andd mer))

MAA2b2 3 isomers are possible (2 cis and 1 trans)


+

NH2

Cl

en
Cl
Co

en

Co

en

en

is

Cl
en
cis

Cl
trans

NH2
28

Optical Isomerism
Optical isomers are related as non-superimposable mirror images and differ in the
direction with which they rotate plane-polarized light. These are possible for both
tetrahedral and octahedral complexes, but not square planar.

Left handed

Right handed

The absence of a plane of symmetry ensures optical activity in most cases

29

Valence Bond Theory


The model utilizes hybridization of metal valence orbitals to account for the observed
structures and magnetic properties of complexes. In transition metal ion containing (n1)d, ns and np undergo hybridization to give hybridized orbitals. An empty hybrid
orbital on the metal center can accept a pair of electrons from a ligand to form a bond.
atomic number
Octahedral complex of [Co(NH3)6]Cl3
of Co 27
4p
3d
4s
d7, 4s2
d 2sp3

[PtCl4]2- which is diamagnetic d8 square planar

[NiCl4]2- which is paramagnetic d8 tetrahedral

electrons from a ligand: given in green color

Co(III) d6 e-

Limitations of Valence Bond Theory

The exhibition of color by coordination complexes is not explained

Quantitative interpretation of magnetic data is not given

Whether a complex of coordination number 4 is square planar or tetrahedral


cannot be exactly predicted

Weak and strong ligands cannot be distinguished

The thermodynamic and kinetic stabilities of complexes are not quantitatively


interpreted

The Nobel Prize in Physics 1977 was awarded jointly to Philip


Warren Anderson,
Anderson Sir Nevill Francis Mott and John Hasbrouck van
Vleck "for their fundamental theoretical investigations of the
electronic structure of magnetic and disordered systems".
When applied to the iron group the results of crystal field theory are particularly
striking and form the basis of much of what may be called modern magnetochemistry.
The crystalline potential is much larger than for the rare earths and is so powerful that
it q
quenches a large
g p
part of the orbital p
part of the magnetic
g
moment even at room
temperatures. Schlapp found that the magnetic behavior in the iron group required a
large crystalline field of nearly (but usually not entirely) cubic symmetry.*
EachtimeIreadthepaperofSchapp andPenneyIamimpressedwithhowitcontains
alltheessentialingredientsofmoderncrystallinefieldtheory,althoughtherehave
b
beenchangesinthebestquantitativeestimateofDin(7c).
h
i th b t
tit ti
ti t f D i (7 )

TheNobelPrizeinPhysics1967wasawardedtoHansBethe"forhis
contributions to the theory of nuclear reactions especially his
contributionstothetheoryofnuclearreactions,especiallyhis
discoveriesconcerningtheenergyproductioninstars".

Krishnan,K.S.andMookherji,A.,Phys.Rev.51,428and774(1937)

32

Crystal Field Theory (CFT)


Proposed by Hans Bethe 1929 and van Vleck developed in 1935
The assumptions of the crystal field theory are as follow:
The interaction between the metal ion and the ligand is
assumed to be purely electrostatic (ionic) in nature.
The ligands are treated as point charges.
N t CFT does
Note:
d
nott allow
ll
f any overlap
for
l between
b t
th metal
the
t l
orbitals and the ligand orbitals.

M-L random interaction

d orbitals

Octahedral Crystal Field splitting

(dx2

y ,

o
M+L
(dxy, dyz, dxz)
spherical
(free-metal
(free
metal ion)

M L6

dz2 )

Octahedral Field
To sum it up...
p
Metal ions are attracted to the electron pairs in ligands
The lone pair of electrons in the ligands repel the electrons present in
the d orbitals
These interactions are called crystal field
Such interactions affect the energy of the d orbitals but not uniformly

E nergy

dx2-y2, dz2

d orbitals in a
spherical field

dxy , dxz, dyz


d orbital splitting in an
octahedral field

d orbitals in a free ion

Crystal Field Splitting in an Octahedral Field

Energy

eg

3/5 or 0.6o

o
Barry centre

2/5 or 0.4 o
t2g

The higher energy set of orbitals (dz2 and dx2-y2) are labeled as eg, a doubly degenerate
(e) orbital with gerade (g) symmetry, and the lower energy set is labeled as t2g , a triply
d
degenerate
t (t) orbital
bit l with
ith gerade
d (g)
( ) symmetry.
t These
Th
notations
t ti
are based
b d on the
th
symmetry of the orbitals.
The energy separation between the two levels is denoted by o or 10 Dq.
To maintain the average energy, the eg orbitals need to be repelled by an amount of 0.6
o and the t2g orbitals to be stabilized to the extent of 0.4 o.

Distribution of electron in an Octahedral Field


eg

eg

Enerrgy

3/5 or 0.6o

3/5 or 0.6o

o
Barry centre

Barry centre
2/5 or 0.4 o
t 2g

2/5 or 0.4 o
t 2gg

This quantity is known as Crystal Field Stabilization Energy (CFSE)


( 2g) + 0.6 x n(e
( g)] o n = number of electrons
Therefore, CFSE = [[-0.4 x n(t
For example in d1 CFSE = [-0.4 x 1 + 0.6 x 0] o = -0.4 o
The energy of d1 electron is -0.4 o.

The complex is stabilized to the extent of 0.8 o.

Thus, the complex is stabilized to the extent of 0.4 o.

Examples: [V(H2O)6]3+

Examples: [Ti(H2O)6]3+

Note: Distribution of electrons ggenerallyy follows Hunds rule of maximum multiplicity


p
y
Electron filling starts with lower orbitals (t2g level first)
What about d4 and other d electron systems?

Distribution of Electrons in an Octahedral Complex


d4
2 u.e.
4 u.e.

There are two possibilities for metal ions having d4-d7


electronic configuration. Depending on the nature of the
ligands and the metal they could be high-spin or lowspin
i complexes.
l
For the d4 system, CFSE =
For high-spin,
g p
((3 0.4)) ((1 0.6)) = - 0.6 o and
for low-spin, (4 0.4)-0 = -1.6 o

d5

1 u.e.

5 u.e.

d6

0 u.e.

4 u.e.

d7

1 u.e.

3 u.e.

Distribution of Electrons in an Octahedral Complex


In all electronic configurations involving two electrons in the same
orbital, the actual CFSE is reduced by the energy spent on pairing the
electrons (P).
For the d4 system, CFSE =
For high-spin, (3 0.4) (1 0.6) = -0.6 o o < P
and
for low-spin, 4 0.4 = -1.6 o (-P) (for 1 electron pairing) o > P
1.6 o P (in some text books including huheey)
Metal ions with 4 7 electrons in the d orbital can exist as high-spin or low-spin
complexes.
Weaker ligands tend to give high-spin complexes,
complexes
whereas stronger ligands tend to give low-spin complexes.
Home work: Calculate CFSE values for both in high and low spin electronic
configuration
f
starting from
f
d3 -dd10
Consider the electron pairing and give the final values including pairing
energy

Octahedron and Tetrahedron inside a cube: A comparison

OCTAHEDRON

TETRAHEDRON
Ligands approach through alternate corners
Absence of centre of symmetry

Tetrahedral Field

Energy

t2

2/5 t

t
3/5 t

Tetrahedral geometry does not containing centre of symmetry


The higher energy set of orbitals (dxz, dyz, dxy) are labeled as t2 and the lower energy
set (dz2 and dx2-y2) is labeled as e.
Electron first fills in the orbitals of e and then to t2

Energyy

Octahedral Vs Tetrahedral

Crystal field splitting in tetrahedral and octahedral complexes are related by


t = 4/9