GC - Quiz 3

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Pilani Campus
CHEM F111 : General Chemistry

Lecture 16
AY: 2021-22, Sem-1
1 BITS Pilani, Pilani Campus

Nuclear Magnetic Resonance
(NMR)
Spectroscopy
NMR spectrometer NMR Spectrum

Why NMR?
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Nuclear Magnetic Resonance
Absorption spectroscopy:
In the energy transfer process, electromagnetic radiation interacts with
either the oscillating electric dipole (electronic, vibrational, rotational
spectra) or the oscillating magnetic dipole (Magnetic Resonance)
• Nuclear: Related to the nucleus of an atom
• Magnetic: Nuclei possessing magnetic dipole
• Resonance: Phenomena of energy absorption by an
oscillating medium, when there is a correspondence
between frequency of oscillating medium and incoming
signal.
• Spectroscopy: deals with the transition induced in a
chemical species by its interaction with the photons of
electromagnetic radiations.
Nuclear Spin, I
• Just like electrons, a nucleus is also spinning

around its own axis.
• The nucleus possess spin angular momentum. The magnitude

of angular momentum could be represented in terms of nuclear
spin quantum number, I.{similar to ‘s’ for spin of an electron!}
• I can take 2I+1 different orientations relative to an arbitrary
axis, which can be defined by a quantum number mI
where mI can take the values = I, I-1……….-I.
mI quantizes the orientation of the nuclear magnetic
moment vector or, gives the no. of allowed spin states.
Nuclear Spin, I
The nuclear spin
states  and  are
degenerate in the
absence of external
magnetic field.
1H, 13C, 19F, 31P, : Nuclei with I = ½ : mI = ½ () , -½ ()

2H (deuterium), 14N: Nuclei with I = 1 : mI = 1, 0, -1
12C, 16O: Nuclei with I = 0 (NMR inactive)
Nuclei in magnetic field
• A nucleus with non zero spin (spinning charge) has a magnetic moment
(μ) and behaves like a tiny magnet (generates a magnetic field).
•The orientation (2I+1) of this magnetic field is determine by the value

of mI.
• On applying an external magnetic field (B), the spinning nuclei will

orient themselves with or against the direction of external magnetic field.

Nuclei in magnetic field for I = 1/2
• On applying an external magnetic field (B), the two degenerate states
(α & β) for I = 1/2 nuclei splits into two non-degenerate energy levels.
•The energy of each level is given by: E = - γN ћ B mI;

m
I
. γN = nuclear gyromagnetic
(or magnetogyric) ratio
Em = - gμN B mI;
I
. g = Nuclear g-factor:
experimentally determined.
μN = Nuclear magneton

Nuclei in magnetic field
Em = - γN ћ B mI = -gNN B mI γN = N gN/ћ
I
gN = 5.586 (1H)
Nuclear magneton
( μN = eћ/2mp)
μN=5.05×10−27 J/T
E= Eβ- Eα = γN ћ B
hγNB ћ
γNB/2
Selection rule: mI = 1
NMR resonance phenomena
• Nuclei starts Precessing.
• Precession of magnetic moment
about external magnetic field
Larmor frequency, γNB/2
• Resonant absorption of EMR will take

place only when the frequency of the
radiation equals Larmor frequency.
• Nuclei excites from state to state by

absorbing energy corresponding to the
radiofrequency region of EMR.
NMR: The technique
• Homogeneous magnetic field:

High fields (superconducting
magnets used)
• A radiofrequency source
• Analyzer
NMR: The technique
• NMR spectrum may be recorded
(i) either by varying radiofrequency keeping magnetic field

constant
(ii) Or varying magnetic field keeping radiofrequency constant

[Continuous wave (CW) technique].
• Typically the radiofrequency ~ 400 MHz (for 1H nuclei) & 100 MHz
(for 13C nuclei) is required if a magnetic field of approximately 9 T.
• FT (Pulse) NMR: A pulse (square wave of finite duration – about a

few microseconds) is used to excite all the nuclei and analyzed
using Fourier Transform technique.

Nuclei Population in two states
• On applying a magnetic field, the
distribution of nuclei in the two energy
states could be estimated using Boltzman
distribution Law.
 E  N B
N
e kT
e kT
N  N   N N
 N 
N 1 
N  N   N N B N N g N B
  
  
N
 N  N 
N  N   N 
2kT 2kT
N 1  
 N 
B = 10 T , T = 293 K ; N = 1000 000 ; γN (Hydrogen nuclei) = 2.67x108 T-1s-1
N - Nβ = 35 (just 35 nuclei excess per million nuclei)
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Sem-1, AY 2021-22,
Lecture 17
Summary of Lecture 16
• Nuclear states results by applying an external magnetic field
B on a large number of magnetic active nuclei (I≠0) and the
nuclei starts precessing with or opposite to B with Larmor
frequency;
γNB/2 or   NgNB/h
• Nuclei in such states gets excited
from lower state to higher state by
absorbing energy corresponding to the
radiofrequency region of EMR at
resonance condition (when the
frequency of the radiation equals
Larmor frequency).
NM Resonance: The phenomena
• Different Nuclei precess with different Larmor frequency at a

particlular external field (B).
γNB/2
Or
 NgNB/h

Nuclei Population in two states
• The distribution of nuclei in the two
energy states, on applying a magnetic
field could be estimated using Boltzman
distribution Law.
 E  N B
N
e kT
e kT
N  N   N N
 N 
N 1 
N  N   N N B N N g N B
  
  
N
 N  N 
N  N   N 
2kT 2kT
N 1  
 N 
B = 10 T , T = 293 K ; N = 1000 000 ; γN (Hydrogen nuclei) = 2.67x108 T-1s-1
N - Nβ = 35 (just 35 nuclei more nuclei per million nuclei)
Intensity of signals
Intensity of Absorption, I  (N  - Nβ) B
(N - Nβ)  B/T → Intensity of Absorption, I  B2/T
• Decreasing T or Increasing B, increases the population difference &
thus the intensity increases.
• In addition, the strength of a signal
are related to the relative abundances
for a particular nucleus.
Isotopic abundance 1H is also very high
(99.98 %) Strong signal (1H) Recorded in
lesser time.
Isotopic abundance 13C is less (1.10 %)

rest is 12C (NMR inactive; I = 0); weak
signal (13C) Recorded in more time.
A typical NMR Spectrum
12C
NMR, 16O NMR
• Ethanol; CH3-CH2-OH
cannot be studied (I = 0)
Recording 13C NMR NMR pertains to
only one type of Recording 1H NMR
B=9T nuclei at a time. B=9T
 ~ 100 MHz (13C)  ~ 400 MHz (1H)
RF source required
Precessional freq. RF source required
 ~ approx. 100 MHz
 ~ approx. 400 MHz
γNB/2
• WHY DIFFERENT
PEAKS FOR DIFFERENT
HYDROGENS
13C NMR of Ethanol (OR CARBONS) ? 1H NMR of Ethanol
Reason for Multiple peaks
Why do we get different peaks for hydrogen
nuclei in the NMR spectrum of a compound?
Why should the hydrogen nuclei in different compounds
behave differently in the NMR experiment ?
• The different Hydrogen nuclei in a molecule are in different
chemical environment.
• Chemically different hydrogens in an organic molecule do not
experience the same magnetic field.
• Now, the electron(s) surrounding the proton in covalent

compounds and ions are charged particles……………………

Shielding constant, 
• ……..The applied magnetic field can induce a circulating motion
of electrons in the molecule, which gives rise to generation of
small magnetic field (Badd). Badd = -B
; Shielding constant; It can be –ve or +ve depending upon

whether the induced field adds to the B or subtracts from the B.
• Nuclei in different chemical environment/groups have different
shielding constants. Thus, the net magnetic field suffered by
each nuclei is Blocal (not B)
Blocal = B + Badd = B(1-) γN Blocal / 2γN B / 2
• Different Nuclei (of the same type in different part of a

molecule) resonate with a different Larmor frequency and thus
will come to resonance at different frequencies.
Chemical Shift
γN Blocal / 2γN B / 2
Resonant frequencies being dependent on strength of external
magnetic field, are inconvenient to remember.
How to get rid of field-dependence?
PLOT OF SPECTRUM COULD BE IN TERMS OF A NUMBER THAT COULD
BE REMEMBERED EASILY RATHER THAN THE EXACT VALUE OF
RESONANT FREQUENCIES FOR NUCLEI ON DIFFERENT ENVIRONMENT.
Measure the difference in the resonant freq. () of a nucleus

with respect to the resonant freq. (0) of the same nucleus of a
standard reference compound.
•REFERENCE COMPOUND: Si(CH3)4 (Tetramethyl silane or TMS) is

commonly used reference in NMR spectra of organic compounds.
Chemical Shift
•TMS: Si(CH3)4 (Tetramethyl silane):
- Volatile compound (can be removed easily)
- Hydrogen Nuclei are highly shielded (Why??)
- Gives a single sharp peak
Hydrogen nuclei are in same chemical environment so all of
them will resonate at same Larmor frequency (0) and we
can set that (0 = 0) as zero (while plotting).
AT B= 9 T, the 1H nuclei of TMS will be resonating exactly

equal to 400 MHz and we have to determine the resonant
frequencies of different 1H nuclei in a compound with
reference to this Larmor frequency of 1H nuclei of TMS.
Chemical Shift
Chemical Shift: Difference between the resonant frequency of a
hydrogen nuclei of a compound with that of hydrogen nuclei in
TMS.
Chemical shift:  = {( – ) /} X 106
Chemical shifts are reported on  scale.……..
[….which is the x-axis in the NMR spectrum]
 : Larmor freq. of 1H
nuclei of TMS
 : Larmor freq. of a
particular 1H nuclei in a
compound.
Shielding/Deshielding
Shielding constant:  = local + neighbour+ solvent
local : due to the shielding from the electrons immediately
surrounding the nucleus. (Electron density around the nuclei)
neighbour : due to the shielding from the neighboring environment.
solvent : the contribution from solvent molecules.
local : (An important factor)
If electron density around the
nuclei is decreased: Nuclei is
deshielded → lower  → higher
Chemical shift (): DOWNFIELD
If electron density around the
nuclei is increased: Nuclei is
shielded → higher  → Lower
Chemical shift (): UPFIELD
Effect of Electron density: local
CH3-H2C-X • More electronegative atoms

deshield more and give
For CH2 nuclei,
as electronegativity of X larger shift values.
increases, electron density
around hydrogen nuclei
decreases, shielding
decreases, deshielding
increases and δ increases.
• Effect of electronegativity
decreases with distance.
Shielding/Deshielding
• Additional
electronegative atoms
cause increase in
chemical shift.

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AY-2021-22, Sem-1
Lecture 18
γN Blocal / 2γN B / 2
Blocal = B + Badd = B(1-)
Shielding constant:  = local + neighbour+ solvent
local : due to the shielding from the electrons immediately
surrounding the nucleus. (Electron density around the nuclei)
If electron density around the If electron density around the
nuclei is decreased : Nuclei is nuclei is increased: Nuclei is
deshielded → Lower local → peak shielded → higher local → peak
observed at higher  : DOWNFIELD observed at Lower : UPFIELD
Chemical shift:  = {( – ) /} X 106

Chemical shift are reported on  scale.……..
[x-axis in the NMR spectrum]
local : Shielding/Deshielding
Depending on their chemical environment, protons in a
molecule are shielded/deshielded by different amounts.
Lower  Relatively
Higher 
• The number of signals

shows how many
different kinds of
protons are present.
TMS • The location of the
signals shows how
shielded or deshielded
each proton is.
(i) Number and (ii) Intensities of peaks
• (i) No. of peaks equals the no. of distinct sets of “equivalent” protons.
• Equivalent Hydrogens have same chemical Shifts.
• (ii) Intensity of a peak is directly proportional to the no. of equiv.
protons responsible for the peak (its given by area under peak).

e.g.: No. of peaks in 1H NMR spectrum
One peak (12H)

Two peaks (6:4)
Four peaks (6:1:2:2) One
peak (9H)
Two peaks (6:2)

One peak (6H) Three peaks
Two major* peaks (5: 1) (3:2:2)
One peak is an overlap of peaks due
to 2 ortho-H, 2-meta-H, 1-para-H
Two peaks
Two peaks (9: 1)
One peak (12H) Two peaks (6:4) (6:1)

neighbour : Effect of neighboring environment.
Benzene ring has an anisotropic magnetic susceptibility.

A ring current is produced due to the applied magnetic field.
Aliphatic-C-H, approx. δ 1-2
Shielded Shielding zone
Induces the field

that reinforces
with the external
magnetic field.
Deshielding zone
Aromatic C-H, approx. δ 7-8
Highly Deshielded
neighbour Effect of neighboring environment.
Similarly, Alkenes & Aldehydic proton shows anisotropic

behavior.
CH=CH-H, approx. δ 5-6 O=CR-H, approx. δ 9-10

Deshielded Highly Deshielded
Solvent Effect of Solvent
• A solvent may influence the local magnetic field experienced
by a nucleus in a variety of ways. Minor effects
Solute –Solvent interactions:
i) Hydrogen Bonding
ii) Lewis acid base complex formation
iii) Solvents such as benzene having magnetic susceptibilities
can provide shielding or deshielding effects.
iv) Steric interactions.
• Deuterium labeled Solvents: Chloroform-d (CDCl3),

deuterium oxide (D2O),
benzene-d6 (C6D6),
acetone-d6 (CD3COCD3)

δ range for different Protons in different
chemical environment

O-H and N-H Signals
• Chemical shift of O-H & N-H depends on concentration & the
solvent used for recording NMR.
• Hydrogen bonding in concentrated solutions deshield the
protons. Hydrogen bonding involves electron clouds transfer
from hydrogen atom to neighboring electronegative atoms.
δ (O-H) in o-hydroxyacetophenone is more deshielded

than δ (O-H) in phenol
• However, δ value of OH/NH may vary in aliphatic or aromatic
systems (no fixed region).
• O-H and N-H peaks are observed as broad peaks.
Examples: No. of peaks In NMR spectrum
• CH3COCH3 CH3CH2OH
Why splitting
of peaks
? ?
?

The fine structure: Spin-spin coupling
The splitting of the groups of resonances (peaks) into individual
lines is called fine structure.
• Nuclei themselves are little magnets they influence each other,
changing the energy and hence frequency of nearby nuclei as
they resonate—this is known as spin-spin coupling.
• This coupling interaction between two nuclei occurs through
chemical bonds, (and can typically be seen up to three bonds
away) results in splitting of spectral lines, called the
multiplicity or splitting or coupling pattern of each signal.
• The strength of interaction is expressed by spin-spin coupling

constant J (Hz): J is independent of magnetic field (B).
The fine structure: Splitting of peaks (AX)
One neighboring X nuclei splits Similarly, one neighboring A
the peak of A into two by a nuclei splits the peak of X into
coupling factor of JAX two by a coupling factor of JXA

The fine structure AX2
1 :2: 1
The two X nuclei may
have the 22 = 4 spin
arrangements.
The middle two
arrangements are
responsible for the
coincident resonance of
A.

The fine structure
AX3
There are 23 = 8
arrangements of the
spins of the three X
nuclei, and their
effects on the A
nucleus gives rise to
four groups of
resonances.
1 :3 : 3 : 1
The fine structure: n + 1 rule
• The proximity of "n" equivalent H on neighbouring carbon
atoms, causes the signals to be split into "n+1" lines.
• Equivalent protons (or those with the same chemical shift)
do not couple to each other.
1 peak (not split) 1 peak (not split)

Singlet, 3H Singlet, 4H
Examples to solve:
Triplet (t): 2 Doublet (d):
Adjacent Protons 1 Adjacent
Proton

Examples to solve:
1:1
1:2:1
1:2

The fine structure: Summary
• The relative intensities of lines within a multiplet is given
by coefficients of the binomial expansion: (x+1)n
• Pascal's triangle
S
Overlap or combination
d of peaks:
t
multiplet (m)
q
quin.
sext.
• A typical Notation of Ethanol:

1H NMR (CDCl3) δ: 4.82 (brs, 1H), 3.86 (q, J = 7.2 Hz, 2H), 1.26 (t, J =
7.2 Hz, 3 H)
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AY 2021-22, sem-1
Lecture 19
• No. of peaks in 1H NMR spectrum equals the no. of distinct sets of
“equivalent” protons.
• Intensity of a peak is directly proportional to the no. of equiv. protons
responsible for the peak (its given by area under peak).
• Chemical Shift: Different δ for 1H nuclei in diff. chemical environment
eg.; Ar-H: δ 6.5 - 8 ; CAlkene-H: δ 5 - 6 ; CAlkyne-H: δ 2.5 - 3.0
CH2-X: 3 - 4 (X: Cl, NH, OH); -CH2-Ar: 2 - 2.5; -CH2-CO: 2 - 2.5
O=C(R)-H: δ 9 - 10; O=C(R)-OH: δ 10 – 12
[OH/NH/NH2]: δ vary in aliphatic or aromatic systems (broad (br) peak)
• Splitting of peaks:The peaks in 1H NMR spectrum are splitted into fine
structures due to spin-spin coupling.
Eg. One neighboring X nuclei splits the peak of A into
two by a coupling factor of JAX & Vice versa
The fine structure: Splitting of peaks (AX)
One neighboring X nuclei splits Similarly, one neighboring A
the peak of A into two by a nuclei splits the peak of X into
coupling factor of JAX two by a coupling factor of JXA

Examples to solve:
1:1
1:2:1
1:2

• The proximity of "n" equivalent H on neighbouring carbon
atoms, causes the signals to be split into "n+1" lines.
• Equivalent protons (or those with the same chemical shift) do

not couple to each other.
1 peak (not split) 1 peak (not split)

Singlet, 3H Singlet, 4H
• The relative intensities of lines within a multiplet is given
by coefficients of the binomial expansion: (x+1)n
• Pascal's triangle
S
Overlapped or
d combination of
t peaks: multiplet (m)
q
quin.
sext.
• A typical Notation of Ethanol:

1H NMR (CDCl3) δ: 4.82 (brs, 1H), 3.86 (q, J = 7.2 Hz, 2H),
1.26 (t, J = 7.2 Hz, 3 H)
NMR Spectrum-Information
PROBLEM SOLVING: Information from 1H-nmr spectra:
1. Number of signals: How many different types of equiv.
hydrogens in the molecule.
2. Position of signals (δ, chemical shift): different chemical
environments for these equiv. hydrogens.
3. Relative areas under signals (integration): How many
hydrogens of each type.
4. Splitting pattern: How many neighboring magnetic active
hydrogen nuclei.

Examples NMR Spectrum
CH3-CH3 CH3-CH2-Cl
quartet, q triplet, t
2 peaks:
1 peak at δ: 0.88 (s, 6H)
1.21 (t, J = 7.2 Hz, 3H)
3.52 (q, J = 7.2 Hz, 2H)
Example: NMR Spectrum
(CH3)2CHOH

Example: NMR spectrum
B(4H)
s
t(1:2:1)
q(1:3:3:1)
A(4H) C (6H)
Relative Ratios of three peaks; 4 : 4 : 6

Example: Spectrum
H3C CH3
s (3H) a a
b
a singlet 6H
b singlet 4H
m or brs (5H)
m: multiplet or brs: broad singlet

Example: NMR Spectrum (DIY)
o-methylbenzyl chloride

Examples to solve: (DIY)
How many peaks will be present in the 1H NMR spectra of the
following molecules? What will be the ratio of intensities?
CH3CHO 2 peaks; d (1:1, 3H), q (1:3:3:1, 1H); [3:1]

CH3COCH2CH3 3 peaks; s (3H), q (1:3:3:1, 2H), t (1:2:1, 3H); [3:2:3]
CH3CH=CHCH3 2 peaks, d (1:1, 6H), q (1:3:3:1, 2H); [3:1]

4 peaks, d(1:1, 6H), multiplet (m, 1H),
(CH3)2CH-CH2CH3 m (1:4:6:4:1, 2H), t (1:2:1, 3H); [6:1:2:3]
CH3COOCH3 2 peaks, s (3H), s (3H); [1:1]
4 peaks, t (1:2:1, 3H), m (1:4:6:4:1, 2H),
CH3CH2CHClCH3 m (1:5:10:10:5:1, 1H), d (1:1, 3H); [3:2:1:3]
C6H6 1 peak (s, 6H)
Labile Hydrogen, so does not
split or undergo splitting
c = monosubst. Benzene (m or brs)
OH b = CH2 (s)
H2C
c = OH (brs)
m, 5H
S, 2H
Brs, 1H

13C-NMR spectroscopy
For 13C, N= 6.7X107 T-1s-1 (4 times less than for 1H)
Resonant frequency or field strength required for CMR has to be 4 times

less than in case of 1H NMR.
Isotopic abundance is 1.11%
CMR signals are about 6000 times weaker than in 1H NMR
Spin-spin coupling of between C-atoms not observed.
However, coupling with protons detectable. (Very strong: J ~ 100-200

Hz).
Proton Decoupling – a secondary RF source irradiates all the protons

so that both the spin states of protons are equally populated (saturation)
– The transitions of protons are so rapid that average coupling from
protons (mI = ½ and mI = -½) (equal to zero) will be detected – as if no
coupling is there

13C-NMR spectroscopy
Ethyl phenyl acetate – proton coupled and decoupled spectra

13C NMR Chemical Shifts
Carbonyl Unsaturated Saturated

Carbons Carbons C-X Carbons TMS
200 100 0
ppm

Proton decoupled 13C NMR of 2-Butanol
d
c b a

13C-NMR Spectrum Example
CH3
7 carbons give 7
signals, but
intensities are not
equal
OH
200 180 160 140 120 100 80 60 40 20 0
Chemical shift (d, ppm)

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Sem-1, AY 2021-22,
Lecture 20
BITSPilani, Pilani Campus
o-methylbenzyl chloride

Labile Hydrogen, so does not
split or undergo splitting
c = monosubst. Benzene (m or brs)
OH b = CH2 (s)
H2C
c = OH (brs)
m, 5H
S, 2H
Brs, 1H

NMR revision and more practice problems
Concept of degree of unsaturation, U
U = ½ [2N4 + N3 – N1 + 2]
Where, N4= no of atoms with valency 4 (usually C)

N3= no of atoms with valency 3 (usually N)
N1= no of atoms with valency 1 (usually H or Halogen)
U = 1  either one double bond or one ring

U = 2  either two double bonds or two rings or one double bond and one ring
etc………

Applications of Degree of unsaturation, U
When molecular formula of a given unknown organic compound is given, use U.

Then, work on determining its structure based on the given NMR data.
e.g.
Q: Find out the degree of unsaturation of: C4H8O2
Soln:
U = ½ [2 x 4 + 0 – 8 + 2]
=1
 either one double bond or one ring

Q: The 1HNMR of C2H4Cl2 shows the following data:
d: 6.0 (q, 1H), 2.0 (d, 3H). Predict its structure.
Soln: CH3-CHCl2

Q: An unknown organic compound has the molecular formula C4H8O2.
Its 1HNMR data is: d 3.1 (q, 2H), 2.1 (s, 3H), 1.5 (t, 3H). Determine its structure.
Ans:

Q: Assign the structure of C9H12S from the following 1HNMR data:
d: 1.20 (d, 6 H, J = 6 Hz)
3.25 (septet, 1H, J = 6 Hz)
7.25 (broad singlet, 5H)
Ans:

Q: A compound with molecular formula C10H10O4 has the following spectral data:
IR (cm-1): 1725 (sharp), 830 (sharp)
1HNMR (d):
3.88 (s, 6 H)
8.08 (s, 4H)
Determine its structure based on the given data.
Soln:

Q: The no. of signals expected from the proton decoupled 13CNMR of
o-, m, and p-dichlorobenzene would be ……………
3 4 2

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Lecture 21
AY 2021-22, Sem-I
Introduction to Coordination Chemistry
BITS Pilani, Pilani Campus
Handout: Inorganic Chemistry portion

Pioneer Scientist, Alfred Werner
❖ Swiss chemist and a professor at the University

of Zurich, developed the basis for modern
coordination chemistry.
❖ Nobel Prize in Chemistry in 1913 for proposing

the octahedral configuration of transition metal
complexes.
Alfred Werner ❖ first inorganic chemist to win the Nobel prize,

and the only one prior to 1973
The contribution in coordination
chemistry by S. M. Jorgensen
at the same time of Warner
Coordination Chemistry: Basic Concepts
• Transition metals act as Lewis acids and form complexes

/complex ions (with net charge)
Fe3+(aq) + 6CN-(aq) → [Fe(CN)6]3-(aq)
Lewis acid Lewis base Complex ion
Ni2+(aq) + 6NH3(aq) → [Ni(NH3)6]2+(aq)
Lewis acid Lewis base Complex ion
Addition Compounds?

Addition Compounds
Stoichiometric amounts of two or more stable compounds

when join together two types of addition compounds are
formed.
(i) Double salts
K2SO4+ Al2(SO4)3+24 H2O → K2SO4.Al2(SO4)3.24 H2O
Double salts lose their identity in solution
(ii) Co-ordination compounds

Fe(CN)2 + 4KCN → Fe(CN)2. 4KCN = K4[Fe(CN)6]
[Fe(CN)6]4- is stable in solution 5 BITS Pilani, Pilani Campus
Werner’s work
❖ Metal ions exhibit two kinds of valence: primary and secondary
[Co(NH3)6]Cl3 or K4[Fe(CN)6]
❖ The primary valence is the number of charges on the complex ion,
Non-directional
❖ The secondary valence is the number of atoms that are directly
bonded (coordinated) to the metal, Directional
❖ The secondary valence is also termed the “coordination number” of
the metal in a coordination complex
Classification of Ligands
Ligands: classified according to the number of donor atoms

An Illustration of Primary and Secondary valency
Conductivity and Cryoscopic Measurement
Formula Cryoscopic Molar Structure
Measurement Conductivity
CoCl3.6NH3 4 particles 6 charges [Co(NH3)6]3+3Cl-
(Yellow)
CoCl3.5NH3 3 particles 4 charges [Co(NH3)5Cl]2+2Cl-
(Purple)
CoCl3.4NH3 2 particles 2 charges [Co(NH3)4Cl2]+Cl-
(Green & Violet)
CoCl3.3NH3 1 particle 0 charge [Co(NH3)3Cl3]
Co(NO2)3.3KNO2 4 particles 6 charges 3K+[Co(NO2)6]3-
Effective Atomic Number (EAN)
Effective atomic number (EAN) rule : based on the octet theory of
Lewis this is the first attempt made by the scientist, Sidgwick to
account for the bonding in complexes
Sum of the electrons on the central atom (Lewis acid) including those
donated from the ligands (Lewis base) should be equal to the number
of elctrons on a noble gas [Cu(CN)4]3-
At. No of Cu = 29, Cu = +1, 4 L = 8 electrons gained
EAN = 29-1+8 = 36 (Atomic No. of Kr) ❖ Gives stable compound
❖ Violated in many places
EAN: few more examples
Atom At. No. Complex Elec. Lost Elec. Gained EAN
Cr 24 [Cr(CO)6] 0 12 36 (Kr)
Fe 26 [Fe(CN)6]4- 2 12 36 (Kr)
Fe 26 [Fe(CO)5] 0 10 36 (Kr)
Co 27 [Co(NH3)6]3+ 3 12 36 (Kr)
Ni 28 [Ni(CO)4] 0 8 36 (Kr)
Cu 29 [Cu(CN)4]3- 1 8 36 (Kr)
Pd 46 [Pd(NH3)6]4+ 4 12 54 (Xe)
Pt 78 [PtCl6]2- 4 12 86(Rn)
Fe 26 [Fe(CN)6]3- 3 12 35
Ni 28 [Ni(NH3)6]2+ 2 12 38
Pd 46 [PdCl4]2- 2 8 52
Pt 78 [Pt(NH3)4]2+ 2 8 84
EAN violations
• [Ni(NH3)6]2+
• EAN = 28-2+12 = 38 # 36 (Kr)
• If we want 36 to be EAN we have to have penta coordination
which leads to an irregular structure
• less stability
• higher coordination with a regular
structure is preferred

Ligand: Definition of Chelate
When more than one atom of the ligand is bonded to the central
metal atom, ring structures are formed. Such ring structured
complexes are called chelates.
[Co(NH3)6]Cl3 or [Pt(NH3)2Cl2]
Stability of Chelates
The chelates are more stable than the normal compounds.
Consider the following square planar complexes
Cu2+ + 2 (en) → [Cu(en)2]2+ (A)
Cu2+ + 4 NH3 → [Cu(NH3)4]2+ (B)
• A and B have same 4 Cu-N bonds
The higher stability of A is due to
i) Two bonds have to be simultaneously broken to detach the ring.
More the rings are formed more will be the stability.
ii) Entropy factors (consider the backward reactions of the
reactions given above).
Chelate formation: Major factor
[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en) [Ni(en)3]2+ + 6NH3
[Ni(H2O)6] + 6NH3 →[Ni(NH3)6]2+ + 6H2O
➢ en and NH3 have similar N-donor environment

➢ en is bidentate and chelating ligand
➢ reaction proceeds towards right, G negative
➢ G = H - TS (H -ve, S ++ve)
➢ reaction proceeds due to entropy gain
➢ S ++ve is the major factor behind chelate effect
No. of Chelate Ring
Stability increases because enthalpy becomes increasingly

negative (increased number of M–N bonds) & entropy increases
Stability of complexes
[Fe(H2O)6]3+ + NCS- → [Fe(H2O)5(NCS)]2+ + H2O

Kf = [Fe(H2O)5(NCS)]2+/ [Fe(H2O)6]3+[NCS-]
Equilibrium constant Kf  formation constant
M + L → ML K1 = [ML]/[M][L]
ML + L → ML2 K2 = [ML2]/[ML][L]
ML2 + L → ML3 K3 = [ML3]/[ML2][L]
MLn-1 + L → MLn Kn = [MLn]/[MLn-1][L]

Stability of complexes
• K1, K2….  Stepwise formation constant.

• To calculate concentration of the final product, use
overall formation constant n:
n = Kf = [MLn]/[M][L]n = K1 × K2 × K3 × …. × Kn
[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en) [Ni(en)3]2+ + 6NH3

Isomerism
Coordination complexes: Isomerism:

Same atomic composition, different
structures

Structural isomer
[CoBr(NH3)5]SO4 [Co(SO4)(NH3)5]Br
Ionization Isomers
[CrCl(H2O)5] Cl2 •H2O [CrCl2(H2O)4] Cl •2H2O

Hydrate Isomers
[Co(NH3)6][Cr(CN)6] [Cr(NH3)6][Co(CN)6]
[Cu(NH3)4][PtCl4] [Pt(NH3)4][CuCl4]
Coordination Isomers
Structural isomer
Linkage Isomers
Ambidenate ligands
CN- through C or N;
SCN- through S or N;
S2O32- through S or O.
Stereoisomers of square planer com.
[Ma2b2]
M=Metal centre;
a and b are monodentate ligands
[Ma2bc]
M=Metal centre;
a, b and c are monodentate ligands
[Mabcd]
M=Metal centre; a, b, c and d are
monodentate ligands
Stereoisomers of Octahedral com.
[Ma3b3]
Facial isomer (fac) Three Meridional isomer (mer) Three

identical ligands occupies one identical ligands occupies a plane
face of the octahedron. passing through the metal atom
(around the meridian of the
octahedron)
Stereoisomers of Octahedral com.
[M(AA)3]
M=Metal centre; AA is a
symmetrical bidentate ligand in
which the two letters A and A are
two similar coordinating atoms
Two Optical Isomers
[M(AB)3]
M=Metal centre; AB is an
unsymmetrical bidentate ligand in
which the two letters A and B are And their mirror images
the two different coordinating Total = 4 isomers
atoms BITS Pilani, Pilani Campus
Bonding in coordination Chemistry: VBT
Fundamentals of VBT:
✓ The ligand must have a lone pair of electrons
✓ Metals must have an empty orbital of suitable energy available for
bonding
✓ Considers the type of orbitals on metals are used for bonding
✓Geometry can be predicted provided magnetic moment is known
(Magnetic criterion of bond type)

Co3+:
[Co(NH3)6]3+ : Inner Sphere complex [CoF6]3- : Outer Sphere complex
d2sp3 hybridization sp3d2 hybridization

Drawbacks of VBT
✓ This theory does not discuss energies of electrons.
✓ The assumptions about the electrons being localized to specific locations
✓ Cannot account for colour of complexes
✓ Cannot account for spectrochemical series and electronic spectra
BITS Pilani
Pilani Campus

Lecture 22
Crystal Field Theory

Discussed topics……
➢ Werner’s work: Coordination sphere, Coordination No, Primary
and secondary valency
2+ Primary valency
[Ni (NH3)6 ] Cl2
Ionization sphere
Central metal ion
Coordination no
Ligands Coordination sphere
or
Complex entity
➢ EAN, EAN violation, Stability of complexes, Effect of chelation,
Chelate formation, and isomerism
Fundamentals of VBT:
✓ The ligand must have a lone pair of electrons
✓ Metals must have an empty orbital of suitable energy available for
bonding
✓ Considers the type of orbitals on metals are used for bonding
✓Geometry can be predicted provided magnetic moment is known
(Magnetic criterion of bond type)

Co3+:
[Co(NH3)6]3+ : Inner Sphere complex [CoF6]3- : Outer Sphere complex
d2sp3 hybridization sp3d2 hybridization

Drawbacks of VBT
✓ This theory does not discuss energies of electrons.
✓ The assumptions about the electrons being localized to specific locations
✓ Cannot account for colour of complexes
✓ Cannot account for spectrochemical series and electronic spectra
Proposed by Hans Bethe in 1929 (CFT)
Modified by J. H. Van Vleck in 1935 (LFT)
Application starts in coordination complexes
in 1950
➢Focuses on d-orbitals
➢ Ligands are considered as point negative charges
➢ Assumes ionic bonding: electrostatic interactions
➢ Electrostatic interactions: metal ions (+ve centre)
attracted to ligands (-ve centre)
Shapes of d-orbital
CFT: Accounts for observed properties of transition metal complexes
focuses on d-orbitals


Octahedral Crystal Field
-
(-) Ligands attracted to (+)
metal ion; provides stability - -
+
- -
d e-’s undergo repulsion by ligands;
Potential energy of d orbitals increases
-
Ligands approach along x, y, z axes
Lobes are directed towards ligands

greater electrostatic repulsion = higher potential energy
Lobes are directed between the ligands

less electrostatic repulsion = lower potential energy
Octahedral crystal field
_ _
d orbital energy levels dz 2 dx2- y2

E isolated
_ _ _
metal ion dxy dxz dyz
_____
Under ligand field
d-orbitals
Metal ion and the nature of the ligand
determines 
d orbital energy levels Crystal field splitting in an
octahedral field
_ _
eg Determined by metal
E _____ O ion and ligand
d-orbitals _ _ _
t2g
In octahedral crystal field

✓ eg orbitals (dx2-dy2, dz2) are along Inter Nuclear Axes (Metal-
Ligand bond axes) : more repulsion : high energy
✓ t2g orbitals (dxy , dyz , dzx) are away from Inter Nuclear Axis
(Metal-Ligand bond axes): less repulsion : low energy
✓ We don’t refer to isolated metal atom/ion any more; The
weighted mean of these two levels is assumed to be zero;
called Bari center.
oct = o = 10 Dq (different notations for the splitting)
__
__ e g
6 Dq
__ 10 Dq = ΔO
E __
_
4 Dq
__ How to estimate ΔO
__
__ t2g electronic spectroscopy
6 Dq = 0.6 ΔO and 4 Dq = 0.4 ΔO

Estimation of o
o can be measured directly from electronic spectra for d1 and d9
systems;
In other dn cases we can obtain it from calculations using the spectral
data.
Consider [Ti(H2O)6]3+, Ti3+: 3d1 therefore, t2g → eg transition
__ __ eg __ __ eg
__ __ __ t2g __ __ __ t2g
Estimation of o
[Ti(H2O)6]3+
o = 20,300/83.7 = 243 kJmol-1
Complex is reddish violet in color;

Yellow and green light are absorbed and
hence the complementary color is seen.
20,300 cm-1 = 492 nm

The magnitude (value) of o depends on
1. Nature/type of the ligand
2. Charge on the metal ion
3. Size of the metal ion; i.e., whether the metal ion belongs to I, II, or
III row transition elements

Nature/type of the ligand
All other factors are SAME, while making comparisons. For Cr3+ (d3 system)
energy
green violet yellow yellow
[CrCl6]3- [Cr(H2O)6]3+ [Cr(NH3)6]3+ [Cr(CN)6]3-

13,640 17,830 21,680 26,280
Maximum Absorption Peak (cm-1) 18 BITS Pilani, Pilani Campus
Color of Transition metal comp
Compounds/complexes that have color:
• absorb specific wavelengths of visible light (400 –700 nm)
• color observed = complementary color of color absorbed
absorbed observed
color color

From the previous data of chromium complexes, we can write the o
value for
Cl- < H2O < NH3 < CN-
weak field strong field
This experimentally determined series is known as spectrochemical
series
o values range from 7000 cm-1 to 30,000 cm-1

• The position of max and hence o varies with the chemical

nature of the ligand
• Ligands causing only a small degree of crystal field
splitting (low o value) are called WEAK ligands
• Ligands causing large crystal field splitting (high o value)
are called STRONG ligands

21
Spectrochemical series
Smallest 
(weak) I- < Br- < S2- < SCN- < Cl- < NO3- < F- < OH- < EtOH (ethanol)
<C2O42- (oxalate) < H2O < EDTA < NCS- < CH3CN < NH3 < en < bipy <
phen < NO2- < PPh3 < CN- < CO (strong) Largest 
➢ There is no visible pattern
➢ No charge or size correlation
➢ Both the sigma and pi bonding nature along with electrostatic
attractions determine the crystal field splitting o
➢ A pattern of increasing sigma donation
Halide donors < O donors < N donors < C donors
Within halide donors for o: I- < Br- < Cl- < F-.
This can be explained in terms of electrostatic repulsions. F- is of
small size and hence more closer bonding and more repulsion
(higher o)

Consider PPh3 < CN- < CO
• o of CN- is almost double that of I- ; This can not be explained by simple
CFT. Covalent bonding of  and  types of bonding is to be included.
• Carbonyl, phosphines are neutral ligands and still produce the maximum
splitting of d orbitals, which implies electrostatic-point charge model is not
sufficient.
 (pi) back bonding from
metal t2g → vacant ligand orbital
PPh3 , CN- , CO are called  acceptors.

Electronic configuration in Oh com.
Expected orbital filling tendencies for e-’s:
✓ occupy a set of equal energy orbitals one at a time (Hund’s rule),
which minimizes repulsions
✓ occupy lowest energy vacant orbitals first
d orbital occupancy depends on Δ and pairing energy, P

• If Δ > P (Δ large; strong field ligand)
➢ e-’s pair up in lower energy d subshell first
• If Δ < P (Δ small; weak field ligand)
➢ e-’s spread out among all d orbitals before any pair up
d orbital occupancy
d1 d2
high spin low spin

d4
<P >P
Nature of metal cation
(i) Different oxidation states of a metal:
Δo for [Fe(H2O)6]2+= 10,400 cm-1
Δo for [Fe(H2O)6]3+= 13,700 cm-1
Higher oxidation; larger splitting i.e., higher Δo value
(ii) Different charges on the cation of different metal: Two different

cation with the same number of d- electrons but with different charge
(metals within a same period):
Δo for [V(H2O)6]2+= 12,400 cm-1
Δo for [Cr(H2O)6]3+= 17,400 cm-1
Size of the metallic species
If all other factors are same, the period to which the metal belongs
matters
Complex o (kJ/mol) Config.
[Co(NH3)6]3+ 296 3d6
[Rh(NH3)6]3+ 406 4d6
[Ir(NH3)6]3+ 490 5d6
➢ Larger the d orbital size it is easier to split

➢ 5d orbitals split larger than 4d orbitals and so on
Tetrahedral complex

Tetrahedral complexes
The direction of approaching ligands coincides with neither eg nor
t2g orbitals.

axial orbital –metal-ligand = 109o28’/2 =  non-axial orbital –metal-ligand
54o44’ = 35o16’
Distance between axial orbital and ligand = distance between non axial orbital
0.707a (a=edge length) (Face of the cube) & ligand = 0.5a (a= edge length)
54o44’

Splitting in tetrahedral complex
d-orbital energy level diagram dxy d d
_ _ _ yz
xz
_ _ 
E dz 2 dx2- y2
isolated
metal ion only high spin
_____
metal ion in tetrahedral
d-orbitals complex
__
__
__ t2
__ 2/5 Δt
E __
_
3/5 Δt
__ e
__
• t2 orbitals are in higher energy as opposed to octahedral field.
• Since there is no centre of symmetry in tetrahedron the parity subscript g
is omitted.
• The total tetrahedral splitting is t
In general t < o ,
• Since there are only 4 ligands compared to 6 in octahedron; this
gives 2/3 reduction from the octahedral crystal field splitting.
• d-orbitals do not coincide with the direction of M-L bonds; this gives
another 2/3 reduction.
So for the same ligand and same metal ion
t = (4/9)o (approximately)
Due to this low t values almost all the tetrahedral complexes are
High Spin (No pairing).
BITS Pilani
Pilani Campus

Lecture 23
Inorganic Chemistry

Octahedral vs. tetrahedral
__ e
__
Tetrahedral Octahedral g
__
t2 __
__ 0.6 ΔO
E 0.4 Δt __
__
_
-0.6 Δt -0.4 ΔO
Free ion __
__
__
__ __ t2g
e
So for the same ligand and same metal ion
t = (4/9)o (approximately)
d6 configuration
Weak Strong
eg t2g6eg0
t2g4eg2 eg
E o E o Octahedron
t2g t2g
e3t23 e3t23
E E
Tetrahedron

Crystal Field Stabilization Energy
In the d1 system, one electron is 0.4 o below Bari Centre. OR this
electron is stabilized with respect to spherically symmetric field.
For an octahedral geometry:
Crystal Field Stabilization Energy = CFSE = (-0.4nt2g + 0.6neg) o ;
n = no. of electrons
[Ti(H2O)6]3+ : CFSE = -0.4 x 1 x o =-0.4x243 = -97 kJmol-1 eg
NOTE: This stability is w.r.t. Bari Centre.
E t2g

CFSE for d-electron
eg
Similarly, V3+ = d2 = t2g So CFSE = - 0.8 o
2
E
t2g
Cr3+ = d3 = t2g3 CFSE = - 1.2 o eg
E
t2g
Hund’s rule of maximum multiplicity is obeyed.

CFSE of d4 configuration
Case I Case II
eg eg
E o E ’o
t2g t2g
Case I: involves pairing which requires energy input

Case II: electron is placed in high energy eg orbital
Note: In both the cases the fourth electron placement raises the
energy of the system
CFSE of d4 configuration
Case I Case II
eg eg
E o E ’o
t2g t2g
o >> ’o
Case I Case II
Pairing energy << o o’ << Pairing energy;
Low spin complex; high spin Complex;
Spin paired complex; spin free complex;
Strong ligands Weak ligands
CFSE for Octahedral complexes
Weak Field Ligand Strong Field Ligand
dn Configuration Unpaired CFSE Configuration Unpaired CFSE
electrons o electrons o
d1 t2g1 1 -0.4 t2g1 1 -0.4
d2 t2g2 2 -0.8 t2g2 2 -0.8
d3 t2g3 3 -1.2 t2g3 3 -1.2
d4 t2g3eg1 4 -0.6 t2g4 2 -1.6
d5 t2g3eg2 5 0.0 t2g5 1 -2.0
d6 t2g4eg2 4 -0.4 t2g6 0 -2.4
d7 t2g5eg2 3 -0.8 t2g6eg1 1 -1.8
d8 t2g6eg2 2 -1.2 t2g6eg2 2 -1.2
d9 t2g6eg3 1 -0.6 t2g6eg3 1 -0.6
d10 t2g6eg4 0 0.0 t2g6eg4 0 0.0
Octahedral CFSE = (-0.4nt2g + 0.6 neg) o
Tetrahedral CFSE = (-0.6ne + 0.4 nt2) t
In octahedral cases, CFSE = 0 for d0, d5(weak) and d10 cases;
In Tetrahedral cases, CFSE =0 for d0, d5 and d10 cases irrespective of

strong or weak field ligands.

Crystal Field Theory: lattice energy
Lattice Energy for transition metal chlorides (1st row transition metals)
Lattice energy: Energy released when
ions come together from infinite
separation to form a crystal
Excess stabilization (-ve) energy
above the line can be from CFSE
d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
Sc2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+
-0.4o -0.8o -1.2o -0.6o 0 -0.4o -0.8o -1.2o -0.6o 0
Crystal Field Theory: hydration energy
M2+(g) + H2O(excess) → [M(H2O)6]2+ H= -ve
Zero CFSE cases (Spherically

symmetric field cases) are d0, d5
(weak) and d10 i.e. Ca2+, Mn2+, and
Zn2+
All other ions have additional
stability which is CFSE

Crystal Field Theory: ionic radii
CRYSTAL FIELD THEORY in explaining variation of Ionic Radii of M2+
ions in Octahedral environment
➢ Ca2+ → Zn2+ nuclear charge increases

➢ Additional electrons are going to the same shell
➢ d electron shielding is poor
➢ Therefore the size of the ions should decrease smoothly
➢ However, as seen in the following graph the radius change is not
smooth
Crystal Field Theory: ionic radii
Ionic radii of the dihalides of
the 1st transition series
Dark circles represents low spin
anions
t2g electrons : not oriented in the direction of metal-ligand bonds.

Less repulsion between the ligand and metal d electrons; closer
bonding and the ionic radius decreases.
V2+ → d3 → t2g3 ; nuclear charge is increased, but the additional
electron goes to t2g only; hence radius further decreases.
Explanation
Cr2+ → d4 → t2g3eg1 (weak field); The fourth electron is now placed in an
orbital directly in M-L bond; repulsion and ionic radius increases
Mn2+ → d5 → t2g3eg2 ; one more electron in eg; hence radius further

increases
Similarly for Fe2+, Co2+, Ni2+ (d6, d7, d8) the additional electrons go to
t2g orbitals and hence the radius decreases
For Cu2+ and Zn2+ the 9th and 10th d electrons go to eg orbital and the
radius increases
Crystal Structure of Spinels: Close-packed Structure

Crystal structure of spinels
Explanation of Crystal Structure of Spinels using CFT:
Spinels, AB2O4: A(II); B(III); O2-
Structure: Cubic Close Packed
Structure of Anions and
cations occupy the empty sites
(holes/ voids)
No. of Tetrahedral sites: 2N

(N= no. of anions per unit cell)
No. of Octahedral sites: N
In normal Spinel: (A2+[B3+2]O42-)

A(II) occupy the tetrahedral sites
B(III) occupy the octahedral sites
Crystal Structure of Spinels:
In Inverse Spinel: (B3+[A2+B3+]O42-)
A(II) occupy the Octahedral sites
B(III) occupy the Octahedral and Tetrahedral sites
Compare the structures of Mn2+Mn23+O4 and Fe2+Fe23+O4
Mn3+ (d4) Mn2+ (d5) Fe3+ (d5) Fe2+ (d6)
CFSE -0.60 Δo 0 0 -0.40 Δo

(Octahedral weak field)
CFSE (Tetrahedral weak field) -0.18 Δo 0 0 -0.27 Δo

Identify the preferred spinel structure for NiFe2O4
Ni is in +2 oxidation state, d8 configuration
In tetrahedral void, configuration: e4t24, CFSE = -0.8 Δt (0.4 ΔO)
In an octahedral void, configuration: t2g6eg2, CFSE = -1.2 ΔO
Fe is in +3 oxidation state, d5 system
In tetrahedral void, Configuration: e2t23, CFSE = 0
In octahedral void, configuration: t2g3eg2, CFSE = 0
Hence, Ni2+ prefer to stay in the octahedral void
Therefore, inverse spinel structure, FeIII[NiIIFeIII]O4
Magnetic property
Weak field Strong field
t2g4eg2 t2g6eg0
eg
eg
d6
t2g t2g
CFSE = -0.4o CFSE = -2.4o
PARAMAGNETIC DIAMAGNETIC
How do we measure the magnetic property??

Magnetic Moments
Weak field Strong field
t2g4eg2 t2g6eg0
eg
eg
d6
t2g t2g
CFSE = -0.4o CFSE = -2.4o
PARAMAGNETIC DIAMAGNETIC
m(spin only) = [4(4+2)]½ BM m(spin only) = 0
= 4.89 BM
Thus, given a value of m and the oxidation state of M, we can find the crystal field d-
electronic configuration as well as the CFSE
Tetragonal distortion
Cube with an octahedron inside Tetragonal system

Stability of a complex
Structure of coordination compounds are determined by two factors
1) Valence Shell Electron Pair Repulsions. These have to be minimized for
a stable structure.
2) Repulsions between non-bonding d-electrons of the metal and the
ligand electrons. These have also to be minimized.
• Regular Octahedron: All the six bond pairs are
placed at similar positions (All bond lengths are
same) (for e.g., SF6).
➢ For the coordination complexes, additionally it
depends on the distribution of the electrons in the
d orbitals
Distortion of Oh complexes
❑ If all the six distances between the ligand and central metal ion are the same are
said to be regular (i.e., symmetrical) octahedral complexes
❑ If the distances are not equal are said to be
distorted octahedral complexes
(a) Diagonally distorted octahedral complexes
- distortion takes place along a two-fold
axis
(b) Trigonally distorted octahedral complexes -
distortion takes place along a three-fold
axis
(c) Tetragonally distorted octahedral
complexes – distortion takes place along a
four fold axis
23
Distortion: tetragonal elongation
Tetragonal complexes may be obtained by any of the following two
ways:
(a) If the two trans ligands lying on the z-axis in an octahedron are
moved away from the central metal cation so that their distance
from the metal cation is slightly greater than it is for the other four
ligands lying in the xy plane, we get a tetragonal structure.
[Cu(NH3)4(H2O)2]2+ has a natural
Two long bonds
distortion due to different kinds of
bonding (Cu-N and Cu-O)
elongated [MnF4Cl2]4- and [MnF2Cl4]4-
Distortion: tetragonal compression
(b) If the two trans ligands located at the z-axis are brought near the
central metal cation so that their distance from the metal cation is
smaller than it is for the other four ligands in the xy plane, we again
get a tetragonal structure.
Two short bonds
compressed

BITS Pilani
Pilani Campus

Lecture 24
Inorganic Chemistry

✓ Application of Crystal Field Theory in understanding

✓ the experimental value of Lattice Energy
✓ variation in hydration energy
✓ variation in ionic radii of the dihalides
✓ structure of spinels
✓ Magnetic property of transition metal complexes

Distortion of Oh complexes
❑ If all the six distances between the ligand and central metal ion are the same are
said to be regular (i.e., symmetrical) octahedral complexes
❑ If the distances are not equal are said to be
distorted octahedral complexes
(a) Diagonally distorted octahedral complexes
- distortion takes place along a two-fold
axis
(b) Trigonally distorted octahedral complexes -
distortion takes place along a three-fold
axis
(c) Tetragonally distorted octahedral
complexes – distortion takes place along a
four fold axis
3
Distortion: tetragonal elongation
Tetragonal complexes may be obtained by any of the following two
ways:
(a) If the two trans ligands lying on the z-axis in an octahedron are
moved away from the central metal cation so that their distance
from the metal cation is slightly greater than it is for the other four
ligands lying in the xy plane, we get a tetragonal structure.
[Cu(NH3)4(H2O)2]2+ has a natural
Two long bonds
distortion due to different kinds of
bonding (Cu-N and Cu-O)
elongated [MnF4Cl2]4- and [MnF2Cl4]4-
Distortion: tetragonal compression
(b) If the two trans ligands located at the z-axis are brought near the
central metal cation so that their distance from the metal cation is
smaller than it is for the other four ligands in the xy plane, we again
get a tetragonal structure.
Two short bonds
compressed

Natural distortion due to different kinds of bondings: No Jahn-Teller Distortion
Example: [MnF2Cl4]4- Example: [MnF4Cl2]4-
Elongation
along z-axis
Compression
along z-axis
Jahn-Teller theorem
In 1937, Jahn-Teller theorem explain why certain six-coordinated
complexes undergo distortion to assume distorted octahedral (i.e.,
tetragonal) geometry.
This theorem states that “any non-linear molecular system possessing
degenerate electronic state will be unstable and will undergo
distortion to form a system of lower symmetry and lower energy and
thus will remove degeneracy”.
NB: Jahn-Teller theorem only predicts the occurrence of a distortion;
it does not predict its nature or its magnitude.


Jahn-Teller distortion

Symmetrical electronic arrangements
Electronic t2g eg Nature of Examples
configuration ligand field
d0 Strong or weak TiO2, [TiF6]2-

d3 Strong or weak [Cr(oxalate)3]3-,
[Cr(H2O)6]3+
d5 Weak [MnF6]4-, [FeF6]3-
d6 Strong [Fe(CN)6]4-, [Co(NH3)6]3+
d8 Weak [NiF6]4-, [Ni(H2O)6]2+
d10 Strong or weak [Zn(NH3)6]2+, [Zn(H2O)6]2+

Asymmetrical electronic arrangements
Electronic t2g eg Nature of ligand Examples
configuration field
d1 HS or LS
d2 HS or LS
d4 Strong field (LS)
d4 Weak field (HS) Cr(II) and Mn(III)
d7 Strong field (LS) Co(II) and Ni(III)
d9 Either strong or Cu(II)
weak
Condition for distortion
No distortion condition: t2g and eg sets as symmetrical orbitals
Condition for slight distortion: When d-orbitals of the central metal

ion of an octahedral complex have t2g orbitals as unsymmetrical
orbitals, there occurs slight distortion in the complex
Condition for strong distortion: When the eg orbitals which point

directly towards the ligands, are unsymmetrical i.e., contain 1, 3, or
2(only in LS complex) electrons, strong distortion

Symmetrically filled orbitals
E
eg eg
t2g t2g
Z-elongation Δo >> δ1 > δ2 Δo >> δ1 > δ2 Z-compression

Symmetrically filled orbitals
The eg and t2g splitting are similar to octahedral splitting
t2g splitting
Consider the t2g splitting in compression; The dxy orbital is lowered

by 2/32 w.r.t. original t2g position and correspondingly the two
orbitals dyz and dxz are raised by 1/3 2
Therefore for symmetric distribution no additional stability arises.

Example of distortion
Consider CrF2 solid
Two different types of bond lengths
Cr-F 1.98 Å (4 bonds)
Cr-F 2.43 Å (2 bonds) Consider CrCl2 solid
Why? Two different types of bond lengths
Cr-Cl 2.39 Å (4 bonds)
Cr-Cl 2.89 Å (2 bonds)
d8 system
Attempts to make [Ni(CN)6]4- always yield [Ni(CN)4]2-
Here o is large and hence 1 is large
and more than the pairing energy
The eg orbital which is occupied
is dz2
This is due to pairing energy < 1

Extreme elongation
In an extreme elongation case

Square planar energy level
x2-y2
xy
z2
xz,yz

d8 square planar system
1) In this case there is no unpaired electron; diamagnetic.
2) dz2 orbital is fully occupied whereas dx2-y2 orbital is completely
free.
3) Ligands approach only through the x,y directions and z direction
is free of ligands due to high repulsion.
4) This gives rise to
Square planar configurations.

d8 square planar system
5) 1 is large in [Ni(CN)4]2- due to CN-. Effect of Ligand field is
manifested here
6) 1 is large in Pt2+, Pd2+ (d8 ) systems due to size of metal ion. Most
of the complexes of these metal ions are square planar in nature
even with weak ligands. manifestation of the effect of the metal
atom/ ion
7) Square planar complexes can thus be assumed to be the extreme
case of tetragonal elongation of octahedron. Two of the octahedral
ligands are at infinite distance from the center of the octahedron.
Square planar energy level
d8 system
CFSEsq. pl.
➢ The dz2 orbital falls the most, as its

electrons are concentrated in lobes
along the z-axis.
Octahedral Square ➢ The dxz and dyz orbitals also drop in
coordination planar energy, but not as much.
coordination ➢ Conversely, the dx2-y2 and the dxy
(xy plane) orbitals increase in energy.
Change in square planar energy level
If the tetragonal distortion (1, 2 ) is large then dz2 orbital can lie
very low.
General Some Co2+, Ni2+,Cu2+ [PtCl4]2-

Preferred geometry of Cu(II) Complex
Cu2+ ion (d9 system) has a much higher CFSE value in a square planar
configuration (CFSE = 1.22 ΔO) than in octahedral (0.6 ΔO) or
tetrahedral configuration (CFSE = 0.18 ΔO)
CFSE values supports why Cu2+ ions forms square planar complexes
rather than tetrahedral or octahedral complexes in both the fields

Square planar system
d4 Cr2+ 4 unpaired electrons ( (dyz, dzx)2 (dz2)1 (dxy)1
d6 Fe2+ 2 unpaired electrons (dyz, dzx)4 (dz2)1 (dxy)1

d7 Co2+ 1 unpaired electron (dyz, dzx)4 (dz2)2 (dxy)1
d8 0 unpaired electrons (dyz, dzx)4 (dz2)2 (dxy)2
Ni2+, Rh+, Ir+ Strong ligands
Au+3, Pt2+, Pd2+ Strong or weak ligands
d9 Cu2+ 1 unpaired electron (dyz, dzx)4 (dxy)2 (dz2)2 (dx2-y2)1
It shows the filling of electrons in the d-orbitals for the complexes shown above if these
would have square planar geometry only.
BITS Pilani
Pilani Campus

Lecture 25
AY 2021-22, Sem-I
Inorganic Chemistry
✓ Tetragonal distortion
✓ Natural distortion
✓ Jahn-Teller distortion
✓ Square planar energy level
✓ Preferred geometry of Cu(II) Complex

Square planar system
d4 Cr2+ 4 unpaired electrons ( (dyz, dzx)2 (dz2)1 (dxy)1
d6 Fe2+ 2 unpaired electrons (dyz, dzx)4 (dz2)1 (dxy)1

d7 Co2+ 1 unpaired electron (dyz, dzx)4 (dz2)2 (dxy)1
d8 0 unpaired electrons (dyz, dzx)4 (dz2)2 (dxy)2
Ni2+, Rh+, Ir+ Strong ligands
Au+3, Pt2+, Pd2+ Strong or weak ligands
d9 Cu2+ 1 unpaired electron (dyz, dzx)4 (dxy)2 (dz2)2 (dx2-y2)1
It shows the filling of electrons in the d-orbitals for the complexes shown above if these
would have square planar geometry only.
Tetrahedral Complexes
Octahedral complexes are preferred for
• 6 bond energies compared to 4 in tetrahedral
• greater CFSE
•Then why Tetrahedral complexes are formed?
❖When the ligands are large and bulky and cause

crowding; In such cases the steric hindrance is of ..
higher energy in octahedral than in tetrahedral.
e. g. triphenyl phosphine

❖Where attainment of regular shape is important.
e.g. compare d7
In a strong octahedral field (t2g)6 (eg)1
Asymmetry in eg → distorted
In a tetrahedral field e4t23
symmetry in e and t2 → Regular
[CoCl4]2- is regular tetrahedron

d0, d2, d5, d7 and d10 configurations of tetrahedral geometry
are regular.

❖When the CFSE is comparable both in octahedral and
tetrahedral geometries.
d0, d5, d10 no CFSE in oct. and tet.

d1 and d6 (weak) has
Oct and Tet CFSE difference
= -0.4 o –(-0.6t) = (-0.4-(-0.6 x(4/9))) o
= (-0.4-(-0.27))o = -0.13 o
Similarly for d2 and d7 cases the difference is

Only –0.17 o

❖When the ligands are weak then  is less and CFSE is less in
value.
If the charge on the metal ion is low (lower oxidation state) then
also  and CFSE are less in value.
That is why many transition metal chlorides, bromides and iodides
form tetrahedral Complexes.

Jahn-Teller distortion in tetrahedral
Are Jahn-Teller distortions possible in tetrahedral environments? Do you think
such distortions are likely to occur? Justify your answer.

Jahn-Teller distortion in tetrahedral
Are Jahn-Teller distortions possible in tetrahedral environments? Do you think
such distortions are likely to occur? Justify your answer.
Jahn-Teller distortions are possible whenever there is a partially filled

degenerate set of energy levels. This can of course occur here if either the e or
t2 levels are only partially filled. However, since neither set of orbitals is
oriented directly towards the ligands, the relative amount of stabilization
gained is smaller than when the eg set is partially occupied in an octahedron so
such distortions are much less likely to occur in a tetrahedral environment

Sample problems
Q: Identify the reason behind distortion in the complexes [MnF 2Cl4]4- and [Mn(CN)6]4-. (ii)
Write their expected geometry (with elongation/ compression) and justify briefly for both
cases.

Sample problems
Q1(i) Identify the reason behind distortion in the complexes [MnF2Cl4]4- and [Mn(CN)6]4-. (ii)
Write their expected geometry (with elongation/ compression) and justify briefly for both
cases.
(i) Natural distortion and Jahn-Teller distortion for [MnF2Cl4]4- and [Mn(CN)6]4-
respectively.
(ii) Tetragonal compression is expected for [MnF2Cl4]4- and tetragonal elongation is
possible for [Mn(CN)6]4-. [MnF2Cl4]4- has a natural distortion due to different kinds of
bonding, (Mn-F and Mn-Cl). As Cl- ligand is larger in size, Mn-Cl bonds will be elongated
resulting in tetragonal compression. In [Mn(CN)6]4- Mn2+ ion is d5 configuration and CN-
is a strong ligand field. So, t2g5eg0, asymmetry in t2g orbital mild Jahn-teller distortion. In
tetragonal elongation CFSE = -2/3ẟ2 but in compression, CFSE = +1/3ẟ2

Understanding the structure of Hemoglobin
Fe2+ nearer to porphyrin ring ; low

spin; eg is unoccupied; shorter ionic
Deoxyhemoglobin, Fe2+ out of plane: high spin, radius for Fe2+; Oxygen is connected
paramagnetic, increase in size but iron is not oxidized to Fe3+.

Comparing CF Splitting (not in syllabus)
Crystal field splitting diagrams for some common fields referred to a common Bary centre. Splittings are given with respect to
o
13
Sample problems
Calculate the tetrahedral CFSE for [FeI4]2- in kJmol-1 which has a

crystal field splitting of 6400 cm-1. Show the electronic
distribution in t2 and e orbitals. What will be the expected
Crystal field splitting value for [FeI6]4-
Solution
[FeI4]2- → Fe2+
Fe atomic No. 26 → …4s23d6
Therefore Fe2+ → 3d6

Sample problems
t e3t3 t = 6400cm-1
=6400/83.7 kJmol-1 =76.4 kJmol-1
Energy
CFSE =(-0.6 x 3 +0.4 x3) t =-0.6 t

e
[FeI4]2- tetrahedral CFSE = -0.6 x 76.4 =- 45.84 kJmol-1

o for [FeI6]4- with the same charge on metal and same ligands
t =4/9 o
o = (9/4) x t = (9/4)x76.4 =171.9kJmol-1

Sample problems
Calculate the approximate Lattice Energy of CoF2 from the following
data: The crystal field splitting for CoF2 is 250 kJmol-1; Lattice energies of
difluorides of Ca, Mn, and Zn are –2600, -2800, -3000 kJmol-1 respectively.

Sample problems
Calculate the approximate Lattice Energy of CoF2 from the following
data: The crystal field splitting for CoF2 is 250 kJmol-1; Lattice energies of
difluorides of Ca, Mn, and Zn are –2600, -2800, -3000 kJmol-1 respectively.
d7 is between d5 and d10 Co2+ → d7 → weak field

t2g5eg2 → CFSE = -0.8 o
Expected lattice energy without =-0.8 x 250
= -200 kJmol-1
CFSE
Actual observed Lattice Energy = -
=-2800+2{-3000-(-2800)}/5 2880 + CFSE
=-2880 kJmol-1 =(-2880 – 200) kJmol-1

= - 3080 kJmol-1
Example: d8 system
[Ni(CN)4]2- - diamagnetic
Here Nickel is in +2 oxidation state;
Ni+2 → d8 and diamagnetic → Square Planar ;
Here this is entirely due to CN- being a strong ligand.
High o ➔ high 1
Ni(CO)4

Example: d8 system
[Ni(CN)4]2- - diamagnetic
Here Nickel is in +2 oxidation state;
Ni+2 → d8 and diamagnetic → Square Planar ;
Here this is entirely due to CN- being a strong ligand.
High o ➔ high 1
Ni(CO)4 - diamagnetic
Here Ni0 → d10 (No 4s electrons)
Therefore, it has to be diamagnetic as there is no unpaired electron in the metal orbitals
It has a tetrahedral geometry (CANNOT BE EXPLAINED BY CFT)

Sample problems
Q2 The general formula of a red-colored Ni(II) complex is NiL(ClO4)2,
where L is a neutral macrocyclic planar ligand as shown next. When the
thiocyanate (SCN–) ions are added, the violet complex NiL(SCN)2 is formed.
Answer the following questions in tabular form.
General formula of Geometry of the Spin-only magnetic moment, Molar

complex complex BM conductivity
NiL(ClO4)2 4 charges
NiL(SCN)2 0 charges

Sample problems
Q2 The general formula of a red-colored Ni(II) complex is NiL(ClO4)2,
where L is a neutral macrocyclic planar ligand as shown next. When the
thiocyanate (SCN–) ions are added, the violet complex NiL(SCN)2 is formed.
Answer the following questions in tabular form.
General formula of Geometry of the Spin-only magnetic moment, Molar

complex complex BM conductivity
NiL(ClO4)2 Square planar 0 4 charges
NiL(SCN)2 Octahedral 2.82 0 charges

Transition metal complexes
One of the most characteristic
chemical properties of these elements
is the occurrence of multiple oxidation
states.
Mn(II) Mn(VI) Mn(VII)
Mn(VII)
Cr(VI)
V(V)
[V(H2O)6]2+
[V(H2O)6]3+
Electronic spectroscopy of complexes
• Studies of electronic spectra of metal complexes provide information about
structure and bonding, although interpretation of the spectra is not always
straightforward.
• Spectra arise because of transition of electrons from one energy level to
another by absorption of EM radiation in the UV-Visible region
• The spectrum of a colored
solution may be measured quite
easily in a spectrophotometer
using the Lambert-Beer’s Law
log10(I0/I) = A
A = ε.c.l
Electronic spectroscopy of complexes
• Absorptions arise from transitions between electronic energy levels:
✓transitions between metal-centred orbitals possessing d-character (‘d–d
transition bands’)
✓transitions between metal- and ligand-centred MOs which transfer charge
from metal to ligand or ligand to metal called charge transfer bands, (CT
bands)
• An absorption band is characterized by both the wavelength (lmax) of the
absorbed EM radiation and emax
• An absorption spectrum may be represented as a plot of absorbance (A)
against wavelength (l) or e against wavenumber , or A against wavenumber
etc.
Electronic spectroscopy of Oh com.
Absorption of radiation leading to electronic transitions within a
molecule or complex
Absorption Absorption [Ni(H2O)6]2+
104 [Ru(bpy)3]2+
10
~14 000 25 000 50 000

200 400 700
visible UV
UV visible
-ν/ cm-1 (frequency)
λ / nm (wavelength)
UV = higher energy transitions - between ligand orbitals
Visible = lower energy transitions - between d-orbitals of transition metals
- between metal and ligand orbitals
Electronic spectroscopy of Oh com.
Absorption maxima in a visible spectrum have three important
characteristics
1. number (how many)
This depends on the electron configuration of the metal centre
2. position (what wavelength/energy)
This depends on the ligand field splitting parameter, Δoct or Δtet and on
the degree of inter-electron repulsion
3. intensity
This depends on the "allowedness" of the transitions, which is
described by two selection rules

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BITS Pilani

CHEM F111 : General Chemistry

1 BITS Pilani, Pilani Campus

NMR spectrometer NMR Spectrum

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• Just like electrons, a nucleus is also spinning

• The nucleus possess spin angular momentum. The magnitude

1H, 13C, 19F, 31P, : Nuclei with I = ½ : mI = ½ () , -½ ()

•The orientation (2I+1) of this magnetic field is determine by the value

• On applying an external magnetic field (B), the spinning nuclei will

7 BITSPilani, Pilani Campus

•The energy of each level is given by: E = - γN ћ B mI;

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• Resonant absorption of EMR will take

• Nuclei excites from state to state by

• Homogeneous magnetic field:

(i) either by varying radiofrequency keeping magnetic field

(ii) Or varying magnetic field keeping radiofrequency constant

• FT (Pulse) NMR: A pulse (square wave of finite duration – about a

12 BITSPilani, Pilani Campus

CHEM F111 : General Chemistry

• Different Nuclei precess with different Larmor frequency at a

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Isotopic abundance 13C is less (1.10 %)

• Now, the electron(s) surrounding the proton in covalent

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; Shielding constant; It can be –ve or +ve depending upon

• Different Nuclei (of the same type in different part of a

Measure the difference in the resonant freq. () of a nucleus

•REFERENCE COMPOUND: Si(CH3)4 (Tetramethyl silane or TMS) is

AT B= 9 T, the 1H nuclei of TMS will be resonating exactly

CH3-H2C-X • More electronegative atoms

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CHEM F111 : General Chemistry

Chemical shift:  = {( – ) /} X 106

• The number of signals

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One peak (12H)

Two peaks (6:2)

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Benzene ring has an anisotropic magnetic susceptibility.

Induces the field

Similarly, Alkenes & Aldehydic proton shows anisotropic

CH=CH-H, approx. δ 5-6 O=CR-H, approx. δ 9-10

• Deuterium labeled Solvents: Chloroform-d (CDCl3),

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δ (O-H) in o-hydroxyacetophenone is more deshielded

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• The strength of interaction is expressed by spin-spin coupling

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1 peak (not split) 1 peak (not split)

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18 BITSPilani, Pilani Campus

• A typical Notation of Ethanol:

CHEM F111 : General Chemistry

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4 BITSPilani, Pilani Campus

• Equivalent protons (or those with the same chemical shift) do