CY 1001: CHEMISTRY:

Structure, Bonding & Reactivity

Teachers
Prof. Beeraiah Baire (BB) (Inorganic & Organic Chemistry)
Prof. G. Ranga Rao (GRR) (Physical Chemistry)

Teaching Assistants (PhD students)

BB part
Poulomi Adak
Sangita Mondal
 Lecture: (CRC 102; C-slot)
Mon: 10:00 - 10:50 am
Tue: 9:00 - 9.50 am
Wed: 8:00 - 8:50 am
Tutorial/Class: (CRC 102)
Friday: 1:00 - 1:50 pm

Classes: 3rd August -13th November 2023 (Last instructional day)

MidSem : xxxxx ( xxxxx ) (40%) (40 + 40 marks)

End-semester : 20th November (9 am – 12 noon) (60%) (60 + 60 marks)
Attendance: 100% (85% minimum)
 CY 1101- Chemistry
(Inorganic & Organic Chemistry)

Dr. Beeraiah Baire

Department of Chemistry, IIT Madras

(Phone: 4206; Office: CB-313; E-mail: beeru@iitm.ac.in)

 Syllabus
BB: Transition Metal Chemistry, Organometallic Chemistry,
Aromaticity, Pericyclic Reactions.

GRR: Chemical Thermodynamics; Chemical Kinetics; Basic

Concepts of Quantum Chemistry
 Inorganic & Organic Chemistry

Transition metal chemistry:

Bonding in transition metal complexes; coordination compounds; crystal field theory, octahedral,
tetrahedral and square planar complexes; CFSE; Jahn-Teller theorem; Spectral, electronic and
magnetic properties of coordination complexes.

Organometallic chemistry:

Synthesis, structure and reactivity of metal carbonyls; 16 and 18 electron rules ; Variety of ligands and
hapticity; Type of reactions: Oxidative addition, Reductive elimination, Migratory insertion;
Homogeneous catalysis, Hydrogenation, Hydroformylation, Monsanto process.

Aromaticity:
Aromatic, non-aromatic and anti-aromatic compounds. Aromatic nucleophilic substitution reactions.

Pericyclic reactions:
Definition, classifications, electrocyclic reaction of butadiene and hexatriene, photochemical [2+2] and
thermal [4+2] cycloadditions, Sigmatropic rearrangements – limited to Cope and Claisen
rearrangements, FMO approach – Woodward Hoffmann rules and basic stereochemistry aspects of
the above reactions.

Text Books:
1. Organic Chemistry by J Clayden, N Greeves and S Warren, 2nd Edition 2012, Oxford University Press.
2. Shriver and Atkin’s Inorganic Chemistry by P Atkins, T Overton J Rourke, M Weller and F Armstrong, 4th Edition
2009, Oxford University Press.
 Physical Chemistry
Chemical Thermodynamics
Second Law of Thermodynamics - Entropy change accompanying various processes (isothermal
expansion, phase transition, heating, entropy of mixing of perfect gases); Absolute entropy and the
Third Law of Thermodynamics; Statistical entropy; Spontaneity of a chemical reaction and Gibbs
energy; Standard Gibbs energies of formation and reactions; Thermodynamic functions (A, G, U & H)
and four fundamental equations, Maxwell relationships; variation of G with T and P, Gibbs-Helmholtz
equation, Chemical potential; G versus extent of reaction (), Equilibrium constant through chemical
potential (gas equilibria), relation between Kp & Kc; Phase equilibria, Gibbs phase rule, phase diagrams
of water and carbon dioxide (supercritical H2O & CO2), Clausius-Clapeyron equation; Liquid-solid phase
diagrams - two-component eutectic systems and cooling curves.

Chemical Kinetics
Parallel, opposing and consecutive reactions; Mechanism of complex chemical reactions; Analysing
mechanisms using the steady-state approximation, Chain reactions (hydrogen-bromine reaction);
Unimolecular reactions (Lindemann-Hinshelwood approach); Transition State Theory for bimolecular
reactions (thermodynamic approach); Enzyme catalysis (Michaelis-Menten Mechanism).
Chemisorption and Langmuir Isotherm.

Basic Concepts of Quantum Chemistry

Uncertainty principle; Motion of a quantum mechanical particle in one dimension; The Schrödinger
wave equation for the hydrogen atom; physical meaning of a wave function, radial wave functions and
probability densities, quantum numbers, wave functions and orbital shapes.

Text Book:
Atkin’s Physical Chemistry by PW Atkins and J de Paula, 8th and 9th Eds., Oxford University Press.
Module 1: Inorganic Chemistry

Part 1: Transition Metal Chemistry

(Five classes)

Part 2: Organometallic Chemistry

(Five classes)
 Transition Metal Chemistry: (Five classes)
(Coordination chemistry)

Bonding in transition metal complexes / Coordination

compounds

Crystal Field Theory (CFT) and splitting of d-orbitals in

octahedral, tetrahedral and square planar complexes

Crystal Field Stabilization Energy (CFSE),

Jahn-Teller Theorem

Qualitative treatment of Spectral, electronic and Magnetic

Properties.
 Elements

Main group elements: groups 1 and 2 (s-block) (except hydrogen), and groups 13 to 18 (p-
block).
(Group 12 elements are usually considered to be transition metals; however, zinc (Zn),
cadmium (Cd), and mercury (Hg) share some properties of both groups, and some scientists
believe they should be included in the main group)
 Elements

Main group elements: groups 1 and 2 (s-block) (except hydrogen), and groups 13 to 18 (p-
block).
(Group 12 elements are usually considered to be transition metals; however, zinc (Zn),
cadmium (Cd), and mercury (Hg) share some properties of both groups, and some scientists
believe they should be included in the main group)
 Transition elements

IUPAC: An element whose atom has a partially filled ‘d’ sub-shell, or which
can give rise to cations with an incomplete ‘d’ sub-shell

or

Any element in the d-block of the periodic table (which includes groups 3 to
12 on the periodic table)

(In actual practice, the f-block lanthanide and actinide series are also
considered transition metals and are called "inner transition metals)

• Filling of electrons in 3d, 4d, and 5d shells

• In s- and p-block, electrons added to outer (valence) shell
• In d-block, electrons added to penultimate shell expanding it from 8-18
• Most elements have incompletely filled d-shell (interesting properties)
 Transition elements
• Metals

• Almost all: HARD, STRONG, High m.p., b.p.

• Conduct heat & electricity

• Form Alloys

• Show variable oxidation states

• At least one of the ions & compounds is colored

• Form paramagnetic species because of partially filed orbitals

• Form coordination compounds (complexes) and organometallic

compounds

• Catalytic property (because of variable oxidation states)

 Variable oxidation states

➢ Increase in the number of oxidation states from

Sc to Mn. All possible states exhibited by only Mn.

➢ Decrease in the number of oxidation states from

Mn to Zn, due to the pairing of d-electrons occurs
after Mn (Hund's rule).

➢ Stability of higher oxidation states decreases

along Sc to Zn (left to right in the period). Mn(VII) and Fe(VI) are powerful
oxidizers. (due to electron pairing and high energy required to lose electrons)

➢ Down the group, the stability of high oxidation states increases (easier
availability of both d and s electrons for ionization).
 Aufbau Principle

Hund's rule: Every orbital in a subshell is singly occupied

with one electron before any one orbital is doubly occupied,
and all electrons in singly occupied orbitals have the same
spin.
 Color

Charge transfer transitions:

➢ Ligand-to-metal charge-transfer (LMCT):
➢ Metal-to-ligand charge transfer (MLCT):
d-d Transitions:
(Coordination complexes/ compounds)
(Coordination complexes/ compounds)
(Coordination complexes/ compounds)
 Transition metal complexes: Examples
Haemoglobin

Oxygen carrier in blood.

Porphyrin-Fe transition metal
complex
Fe(II) ion is octahedrally coordinated.
Coordination number 6

Cis-platin [PtCl2(NH3)2]

square planar Pt(II); CN : 4

cis-isomer: is the first of a series of platinum coordination complex-based
anti-cancer drugs (Platinol-AQ)
 Transition metal complexes: Examples

Vitamin B12, also called cobalamin.

Transition metal complexes / Coordination complexes: Examples
 What is Coordination?

When an orbital from a ligand with lone pairs in overlaps with an empty
orbital from a metal

M L

So ligands must have lone pairs of electrons.

Sometimes called a coordinate covalent bond

 Metal-Ligand Bond

This bond is formed between a Lewis acid and a Lewis base.

➢ The ligands (Lewis bases) have nonbonding electrons.
➢ The metal (Lewis acid) has empty orbitals.
 Structures of Transition Metal Complexes
(Coordination chemistry)

Coordination number (C.N.):

structure is first described by its coordination number, the number of ligands
attached to the metal (more specifically, the number of donor atoms)

The C.N. and structure are determined by

a) size of the central metal
b) the number of d-electrons
c) steric effects arising from the ligands

➢ Complexes with C.N. between 2-9 are known.

➢ In particular, 4 to 6 coordination are the most stable,
(electronically and geometrically)
 Structure of 4 - 6 coordination Metal Complexes
(Most Common Geometrics ) Cordination Number (CN) 5

Cordination Number (CN) 4

Cordination Number (CN) 6

Most Common Geometrics of Transition Metal Complexes
 Structure of 2,3,7,8 & 9 coordination Metal Complexes

CN: 3 CN: 7
CN: 2

CN: 8
CN: 9
 Ligands (complexing agents)
➢ The molecules or ions coordinating to the metal are the ligands

➢ They are usually neutral or anions and polar molecules

➢ The must have lone pairs to interact with metal

➢ Ligands may be attached to metal by a single atom (single dentate

ligands)

➢ Ligands may be attached to metal by a two or three atoms

(bidentate, tridentate, etc.)

➢ Polydentate ligands are called Chelating ligands

Monodentate ligands
 Polydentate Ligands (Chelating ligands)

Bidentate Ligand (Neutral): 2 donor atoms

Ethylene
Diamine (ED)

Bidentate Ligand (anion): 2 donor atoms Bidentate Ligand (Neutral / anion)

Tridentate Ligand (Neutral): 3 donor atoms Tetradentate Ligand (Neutral): 4 donor atoms
 (Pauling 1930)

➢ L to M dative bond, can not explain color (co-ordinate covalent bond)

 Crystal Field Theory (CFT; (Bethe 1929) )
Consequence of metal ligand repulsion

✓ Coulomb Interactions/ ionic bond rather than covalent bond

✓ Attraction between metal ion (metal atom) and ligand electrons
✓ Repulsion between metal electrons and ligand electrons
✓ Can account the color, and temperature dependent magnetic
behavior
Adjusted crystal field theory (ACFT; Van Vleck 1935)
(MO Theory) Overlap of orbitals between ligands and metal
 Crystal Field Theory (CFT; (Bethe 1929) )
Consequence of metal ligand repulsion

❖ The d-orbitals of a free metal ion are degenerate (i.e., the

energy levels are same).
❖ There is an increase in the energy of d- orbitals due to the
repulsion caused by the incoming ligands.
❖ The magnitude of the increase in energy is NOT equal for all
the five orbitals. Thus, the d- orbitals in the complexed metal
ion are NOT equally energetic i.e., non-degenerate.
❖ Depends on the geometry
 Orbitals
An atomic orbital is a mathematical function that describes the
wave-like behavior of either one electron or a pair of electrons in an
atom. This function can be used to calculate the probability of
finding any electron of an atom in any specific region around the
atom's nucleus.

s- orbital

p- orbitals
 d- orbitals
Degenerate (carries same energy) in a free metal ion/atom

t2g

eg

(comes from spectroscopy

and quantum mechanics)
Five d-orbitals with combination diagram
showing how they fit together
Octahedral Complexes
The energy of d-orbitals in presence of octahedral crystal field

(Energy
conservation law)

(Energy
conservation law)
 Crystal Field Splitting Energy or
Crystal Field Stabilization Energy
(CFSE):
The separation between the two sets of orbitals, t2g and eg, is CFSE

(g-represents
point of
Inversion or
inversion
center in the
molecule)

➢ Dq is differential of quanta and is the ligand field splitting parameter.

❖ Ligands effect on CFSE is given by the spectrochemical series (a
list of ligands in order of ligand-field strength)
❖ Ligands with strong pi-acceptor (plus sigma-donor) capabilities are
strong-field ligands (e.g., CO)
❖ Ligands with pi-donor abilities (halides) are weak-field ligands and
others with pure sigma-donor (NH3, H2O) capability are moderate-
field ligands
❖ All ligands are sigma-donors
Basically, all ligands are sigma donors but some of them can be pi
donors/acceptors in addition.

How can you tell

❖ a) has only 1 electron pair at coordinating atom? Sigma-donor
❖ b) has more than 1 electron pair at coordinating atom? sigma and
pi-donor
❖ c) has double or triple bond at coordinating atom? Sigma-donor
and pi-acceptor
❖ d) If the ligand coordinating by phosphorous? Sigma-donor and
d-acceptor
 (size of halide and pi-donors)

(sigma-donor;
(weak pi-donor) (sigma-donor; O) (sigma-donor; N)
pi-acceptor)
Do increases with increasing oxidation number of the metal. This is due to the
smaller size of the ion, resulting in smaller metal to ligand distances, and hence,
a greater ligand field (repulsive interactions between electrons of metal and
ligand increases).
Do increases as you go down a group. This is due to the better bonding ability
of expanded shells using the 4d or 5d orbitals.

1st row TM 2nd row TM 3rd row TM

 High-spin and low-spin complexes (octahedral)
d1-d3 : Metals-ion systems, Hund’s rule predicts that electrons will
not pair until all the t2g (degenerate) orbitals are equally occupied

d1-d3 has only

One type of
possibility.

D4- d7:
Electron configurations can in principle be in high- or low-spin states

d4 system: the fourth electron has two options; it can go in an eg

orbital so all four electrons are occupying orbitals singly; this is high-
spin (HS d4). Or it could go into a t2g orbital where it will pair up with
another electron; this is low-spin (LS d4)
d5 system:

d6 system:

D8-d10 has only one

type of possibility.

d7 system:
D4- d7: high- or low-spin configuration?

(i) Crystal Field Splitting Energy (Δo)

(ii) Pairing energy (P) (The spin-pairing energy (P) is the increase
in energy that occurs when an electron is added to an already
occupied orbital)

When the Δo < P: a high-spin configuration occurs which produces

complexes with the maximum number of unpaired electron spins

When Δo > P: a low-spin configuration occurs which produces

complexes with the minimum number of unpaired electron spins
 Crystal Field Stabilization Energy

CFSE for octahedral complexes can be calculated

using the following equation

CFSE = {-0.4 x n(t2g) + 0.6 x n(eg)}Do + mP

where,
n(t2g) = number of electrons in t2g orbitals
n(eg) = number of electrons in eg orbitals
m = number of electron pairs (excluding natural pairs)
P = pairing energy
Calculated CFSE values for metal-ions with d1-d10 electron configuration

CFSECFSE
= -0.4 Do do
= 0.4 = -4 Dq
Calculated CFSE values for metal-ions with d1-d10 electron configuration

CFSE = -1.2 Do = -12 Dq

Calculated CFSE values for metal-ions with d1-d10 electron configuration
Calculated CFSE values for metal-ions with d1-d10 electron configuration

CFSE = -0.6 Do = -6 Dq CFSE = -1.6 Do + 1P

Calculated CFSE values for metal-ions with d1-d10 electron configuration
For select metal complexes, the following Table lists values of
pairing energy (P), Do, CFSE and resulting spin-state
 t2-orbitals are repelled
more than e-orbitals
(reversal of Octahedral)
(g-represents point of inversion)
Distortions in Octahedral complexes

Jahn-Teller Distortion

1 Angstram (10-10 m) = 100 picometers (10-12 m)

➢ Cu2+ = d9 system, distortion (eg orbitals, unequally filled)
➢ Ni2+ = d8 system, no distortion (eg orbitals, equally filled)
Jahn-Teller Distortion

D9-configurations
➢ Cu2+ = d9 system, distortion (eg orbitals, unequally filled)
➢ Advantage of more (4) electrons in low energy level (at t2g) hence
prefers elongation over the compression
▪ Advantage of the only (1) electron in non-degenerate low energy
level (t2g) hence prefers compression over the elongation
➢ d9 = 4e- are in low energy state (at t2g), and only one e- is in high energy
state (at eg) instead of three. (Oh vs elongation)
➢ d1 = 1e- is in lower energy with only one orbital (if it is Z-compression)
➢ Whereas 1e- is in lower energy with two degenerate orbitals (if it is Z-
elongation)
Oh E Oh E Oh

C E Oh
 Oh Oh

Oh Oh
Find out Elongation or Compression?
➢ Jahn-Teller distortions can be observed using a variety of spectroscopic techniques. In UV-
VIS absorption spectroscopy, distortion causes splitting of bands in the spectrum due to a
reduction in symmetry.

➢ Consider a hypothetical molecule with octahedral symmetry showing a single absorption

band. If the molecule were to undergo Jahn-Teller distortion, the number of bands would
increase.
 Square Planar

elongated

Spherical
environment
 DT < Do < Dsp
(Δt < 4/9 Δo) (Dt) is lower (by ~45%) than in the octahedral case

Square planar geometry achieves much higher stabilization nearly

twice that of Oh geometry
 Magnetic properties
Transition metal-ions and complexes are paramagnetic since they contain unpaired electrons.

Magnetic moment values can be used to tell if a complex is high or low spin.

Magnetic moments can be calculated by magnetic susceptibility measurements.

The formula used to calculate the spin-only magnetic moment can be written in two forms; the
first based on the number of unpaired electrons, n, and the second based on the total electron
spin quantum number, S. Since for each unpaired electron, n=1 and S=1/2 then the two formulas
are clearly related, and the answer obtained must be identical.

μso= √n(n+2) B.M. or μso= √4S(S+1) B.M.

Magnetic moment values can also be used to distinguish between square planar and tetrahedral
geometries.

Square planar complexes are nearly always low-spin d8 (diamagnetic).

If a four-coordinate compound is paramagnetic it is probably tetrahedral. - e.g. Ni(CN)42- (square

planar) is diamagnetic, but NiCl42- (tetrahedral) is paramagnetic.
 Calculated spin-only magnetic moments for some octahedral complexes
Ion d-Configuration μso / B.M.
Ti(III) d1 (t2g1) √3 = 1.73
V(III) d2 (t2g2) √8 = 2.83
Cr(III) d3 (t2g3) √15 = 3.88
Cr(II) d4 high spin (t2g3 eg1) √24 = 4.90
Cr(II) d4 low spin (t2g4) √8 = 2.83
Mn(II)/ Fe(III) d5 high spin (t2g3 eg2) √35 = 5.92
Mn(II)/ Fe(III) d5 low spin (t2g5) √3 = 1.73
Fe(II) d6 high spin (t2g4 eg2) √24 = 4.90
Co(III) d6 low spin (t2g6) 0
Co(II) d7 high spin (t2g5 eg2) √15 = 3.88
Co(II) d7 low spin (t2g6 eg1) √3 = 1.73
Ni(II) d8 (t2g6 eg2) √8 = 2.83
Cu(II) d9 (t2g6 eg3) √3 = 1.73
 Color of Transition Metal Complexes

Why we see Color for an object?

When a sample absorbs light, what we see is the complimentary

color, i.e., sum of the remaining colors that strikes our eyes.

If a sample absorbs all wavelength of visible light, none reaches

our eyes from that sample, and then the sample appears black.

If the sample absorbs no visible light, it is white or colorless.

When the sample absorbs a photon of visible light, it is its
complementary color we actually see.

For example, if the sample absorbed orange color, it would

appear blue; blue and orange are said to be complementary
colors.
 The Color Wheel
The visible part of the electromagnetic spectrum contains light of wavelength 380-
750 nm.

The color wheel below gives information on the wavelength of different color and
also the complementary color.

For example: If red light is absorbed, the complex appears green; If purple light is
absorbed, the complex appears yellow.
 Why we see Color in TM-complexes?

Charge transfer transitions:

➢ Ligand-to-metal charge-transfer (LMCT): An electron jump from ligand
orbital to a metal orbital transition (metal is in a high oxidation state).
➢ Metal-to-ligand charge transfer (MLCT): transition will be most likely when
the metal is in a low oxidation state and the ligand can be easily reduced.

d-d Transitions:
✓ An electron jumps from one d-orbital to another.
✓ In complexes of the transition metals, all the d orbitals do not have the
same energy.
✓ The pattern of splitting of the d orbitals can be calculated using crystal
field theory.
✓ The splitting depends on the particular metal, its oxidation state and the
nature of the ligands.
➢ The color of coordination complexes arises from electronic transitions between levels whose
spacing corresponds to the wavelengths available in the visible light.
➢ In complexes, these transitions are frequently referred to as d-d transitions because they involve
the orbitals that are mainly d in character (for examples: t2g and eg for the octahedral complexes
and e and t2 for the tetrahedral complexes).
➢ Obviously, the colors exhibited are intimately related to the magnitude of the spacing between
these levels.
➢ Since this spacing depends on factors such as the geometry of the complex, the nature of the
ligands, and the oxidation state of the central metal atom, variation on colors can often be
explained by looking carefully at the complexes concerned.
Color of Transition Metal Complexes

[Zn(H2O)6]2+
colorless

The green color of

[Ni(H2O)6]2+ turns blue
when ammonia is added
to give [Ni(NH3)6]2+.

Many of these facts

can be rationalized
from CFT
Ni+2 = d8 ion
 Laporte Rule

In a molecule or ion possessing a centre of symmetry (for octahedral the ‘g’ symbol
refers to center of symmetry), transitions are not allowed between orbitals of the
same parity, for example d to d.

In other words, there must be change in parity (Dl=±1), i.e. the orbital quantum
number should differ by 1.

The forbidden transitions are s → s, d → d

The geometries affected by this rule include octahedral and square-planar

complexes.

The rule is not applicable to tetrahedral complexes as it does not contain a center of
symmetry, and hence d → d transitions are Laporte allowed.

Δl = +/- 1 The Orbital Rule (Laporte rule)

 Spin selection rule

➢ The spin cannot change during an electronic transition.

➢ Promotion of an electron can only proceed if the spin orientation is conserved, i.e. DS = 0.

Illustration of (a) spin-allowed, and (b) spin-forbidden transitions for Ni(II), & Mn(II)
 Spin selection rule

For example, [Ni(NH3)6]2+, d8 system, has two-unpaired electrons and the total spin in
the ground-state is, S = 1.

In the excited state, the number of unpaired electrons remains the same and hence
the total spin, S = 1.

The net change in the spin, between the ground and excited state, DS = 0; so, the
transition is spin-allowed.

On the other-hand, in case of [Mn(H2O)6]2+, d5 (high-spin), the net change in the spin,
between ground and excited state, DS = 1, making it spin-forbidden
 For some common examples possessing octahedral and tetrahedral geometries,
the magnitudes of colors governed by different selection rules are provided in Table

KMnO4 tetrahedral complexes

The magnitude of colors and applicable selection rules for some typical examples
(a) [Ti(H2O)6]3+ ion absorbs light in visible region and produces transition, (b) its
absorption spectrum
These high spin and low spin states of an octahedral complex will have the same energy
when Do = P.
In octahedral field, if the energy of the two spin states is same or nearly same, the low
spin and high spin states can coexist in equilibrium.
This phenomenon is referred to as spin-state equilibrium; the magnetic moment for
these complexes will be anomalous.
An example of metal ion that can exist in HS or LS state in octahedral ligand field is Fe2+ .

If the ground state of the complex is low spin,

(i) An increase in temperature will increase in the population of the high spin state,
i.e., the magnetic susceptibility will increase, and
(ii) A decrease in temperature will increase in the population of the low spin state, i.e.,
the magnetic susceptibility will decrease.

On the other hand, if the ground state is high spin, then the reverse of (i) and (ii) will
hold true.
 [Fe(phen)2(NCS)2]
T (K)

The most interesting example of spin crossover is [Fe(phen)2(NCS)2] complex. At high

temperature this complex exists as high spin with four unpaired electrons. But as the
temperature is lowered, a sharp drop in magnetic moment is observed at 175K and the
low spin form of the complex becomes dominant. This indicates that at 175K,
[Fe(phen)2(NCS)2] exist as both high spin and low spin complex. Thus, the magnetism
of Fe(phen)2(NCS)2 changes sharply at 174K.