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Crystal
y Field Theory
y
CFT takes an electrostatic approach to the
interaction of ligands (as negative point
charges) and to the central metal ions.

Shriver and Atkins: Inorg. Chem., 4thEd.

Rajakumar. A
Topic-II: 2019

Limitation of VB theory

Follow up CFT
• 1929 Hans Bethe - Developed Crystal Field Theory (CFT)
and then
• 1932 J. H. Van Vleck – Used CFT to interpret properties of
transition metal complexes

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Crystal Field Theory

• Charge of Central metal ion

• Size of the Metal ion and

• Strength of the approaching negative

charge of the ligand

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In Octahedral Field
dyz

dz 2

dxz

dx2-y2

dxy

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d-Orbital Splitting Oh

__ __ e
g
dz2 dx2-y2
0.6∆o
__ __ __ __ __ ∆o
Spherical field __ -0.4∆
__ o __ t
2g
dxy dxz dyz
Octahedral field

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Are the ∆td and ∆oh comparable

∆td = 4/9 ∆oh

Reasons?
 Only 4 ligands in the td, hence, field is 2/3 of Oh.

 Direction of ligand approach in td does

not coincide with the d-orbitals, which reduces the
field by a factor 2/3.

Therefore, ∆t is roughly 2/3 x 2/3 = 4/9 of ∆o

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Colour and d-Orbital Splitting

Splitting due to the nature
of the ligand can be obs. &
measured by
Spectrophotometer.

Smaller ∆o =

Larger gaps = shift to

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Origin of Colour
The origin of the color of the transition
metal compounds
p

E2

E h

E1

E = E2 – E1 = h
Ligands influence O, therefore the colour

The optical absorption spectrum of [Ti(H2O)6]3+

Assigned transition:
eg t2g
This corresponds to
the energy gap
O = 243 kJ mol-11

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Spectrochemical Series
Complexes of
cobalt(III) show shift
in color due to the
variation of ligand.

(a) CN–, (b) NO2–, (c) phen, (d) en, (e) NH3,
(f) gly, (g) H2O, (h) ox2–, and (i) CO3 2–.

Spectrochemical Series: An order of ligand

field strength based on experiment

Weak Field I-  Br- S2- SCN- Cl- NO3-

 F-  C2O42-2  H O NCS- CH CN
2 3
NH3 en  bipy phen NO2-
PPh3 CN- CO
Strong Field

H2 N NH2
N
N N N
Ethylenediamine (en)
2,2'-bipyridine (bipy) 1.10 - penanthroline (phen)

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[CrF6]3- [Cr(H2O)6]3+ [Cr(NH3)6]3+ [Cr(CN)6]3-

As Cr3+ goes from being attached to a weak field

ligand to a strong field ligand,  increases and the
color of the complex changes from green to yellow
yellow..

Colour

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Ligand Field Strength

Observations
1. ∆o increases with increasing oxidation
number on the metal
metal.
Mn+2<Ni+2<Co+2<Fe+2<V+2<Fe+3<Co+3
<Mn+4<Mo+3<Rh+3<Ru+3<Pd+4<Ir+3<Pt+4

2 ∆o increases
2. i with
ith iincreases going
i d down a
group of metals.

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Copper(II) Solution
• If you add an excess of ammonia solution
t hexaaquacopper(II)
to h (II) iions iin solution
l ti

Absorbing in….

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Colourless?
• For example, although scandium is a
member
b off the
th d bl
block,
k itits iion (S
(Sc3+) hasn't
h 't
got any d electrons left to move around.

• In the zinc case, the 3d level is completely

full - there aren
aren'tt any gaps to promote an
electron in to. Zinc complexes are also
colourless.

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Distortion in Octahedral Systems

Distortion in Octahedral Systems

• Distortion from ideal Octahedral Environments,
causes different orb. Energy levels.
• When we pull away one ligand (along z-
z axis); then
ultimate removal gives 5-coord. Square Pyramidal.
This partly removes unfav. Interaction in Z-
direction.

All oribtal with z-component (dz2, dxz and dyz) will

fall-in energy.
The other orbitals (non z-components) will go-up in
energy.

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Square Planar

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d9 system

d7 system (low spin)

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d4 system (high spin)

H.W. 1. Identify the J.T. Distortion for Low Spin Complexes

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H.W. 2. Identify the J.T. Distortion for High Spin Complexes

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• The magnetic moment  of a complex with total

spin quantum number S is:
•  = 2{S(S+1)}1/2 B (B is the Bohr magneton)
• B = eh/4me = 9.274 10-24 J T-1

• Since each unpaired electron has a spin ½,

• S = (½)n, where n = no. of unpaired electrons

•  = {n(n+2)}1/2 B

n = no. of unpaired electrons

 = {n(n+2)}1/2 B
Ion n S /B Experimental
Calculate
d
Ti3+ 1 1/2 1.73 1.7 – 1.8
V3+ 2 1 2.83 2.7 – 2.9
Cr3+ 3 3/2 3.87 3.8
Mn3+ 4 2 4.90 4.8 – 4.9
Fe3+ 5 5/2 5.92 5.3

Similar Calculation can be done

for Low-spin Complex

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• In d4, d5, d6, and d7 Oh complexes, magnetic

measurements can very easily predict weak versus
strong field.
• Tetrahedral complexes:
p only
y H.S. complexes,
p ,
• for t  O.
Limitations of CFT
Considers Ligand as Point charge/dipole only
Does not take into account of the overlap of ligand and
metal orbitals

Consequence
e.g. Fails to explain why CO is stronger ligand than CN- in
complexes having metal in low oxidation state

H. W. 1: Explain the enthalpy of hydration of

transition metal ions from the given graphical
report.

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H.W. 2: In case of strong field ligand (CN-)

ionic radii of M2+

Chelate Effect?

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Complexes: Have metal ion (can be zero oxidation state)

bonded to number of molecules/ions (i.e. ligands
ligands)).

Lewis acid = metal = center of coordination

Lewis base = ligand = molecules/ions covalently bonded to
metal in complex

The term ligand (ligare [Latin], to bind)

bind) was first used by
Alfred Stock in 1916 in relation to silicon chemistry. The first use
of the term in a British journal was by H. Irving and R.J.P. Williams
in Nature
Nature,, 1948, 162, 746.

For a fascinating review on 'ligand' in chemistry - Polyhedron, 2, 1983, 1-7.

Teeth of a ligand ( teeth  dent)

• Ligands
– classified according to the number of
donor atoms
– Examples
• monodentate = 1 chelating
• bidentate = 2
agents
• tetradentate = 4
• hexadentate = 6
• polydentate = 2 or more donor atoms

monodentate, bidentate, tridentate etc. where the concept of

teeth (dent)
is introduced, hence the idea of bite angle etc.

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oxalate ion
ethylenediamine
O O 2-
CH 2 CH 2
C C H2N NH 2
O O * *
* *

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Coordination Equilibria & Chelate effect

"The adjective chelate, derived from the great claw or chela (chely - Greek)
of the lobster, is suggested for the groups which function as two units and
fasten to the central atom so as to produce heterocyclic rings."

J. Chem. Soc., 1920, 117, 1456

Ni2+

The chelate effect or chelation is one of the most important ligand effects in
transition metal coordination chemistry.

Coordination Equilibria & Chelate effect

[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]

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Coordination Equilibria and Chelate effect

• K1, K2….  Stepwise formation constant.

• To calculate concentration of the final
product, use overall formation constant
 n:

• n = [MLn]/[M][L]n
• = K1 x K2 x K3 x …. x Kn
∆G⦵ = -RTln(β)
∆G⦵ = -2.303 RTlog10(β)
∆G⦵ = ∆H⦵ - T∆S⦵

Example: [Cd(NH3)4]2+

Cd2+ + NH3  [CdNH3]2+ K1 = 102.65

[CdNH3]2+ + NH3  [Cd(NH3)2]2+ K2 = 102.10

[Cd(NH3)2]2++ NH3  [Cd(NH3)3]2+ K3 = 101.44

[Cd(NH3)3]2++ NH3  [Cd(NH3)4]2+ K4 = 100.93

Overall: Cd2+ + 4 NH3  [Cd(NH3)4]2+

β4 = K1 x K2 x K3 x K4
= 10(2.65 + 2.10 + 1.44 + 0.93) = 107.12

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What are the implications of the following results?

NiCl2 + 6H2O  [Ni(H2O)6]+2

( 2O))6]+2 + 6NH3  [[Ni(NH

[[Ni(H ( 3)6]2+ + 6H2O g  = 8.6
log

[Ni(H2O)6]+2 + 3 NH2CH2CH2NH2 (en) log  = 18.3

[Ni(en)3]2+ + 6H2O

[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en) log  = 9.7

[Ni(en)3]2+ + 6NH3

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Complex Formation: Major Factors

[Ni(H2O)6] + 6NH3
[Ni(NH3)6]2+ + 6H2O

 NH3 is a stronger (better) ligand than

H 2O
 O NH3 > O H2O
 [Ni(NH3)6]2+ is more stable
 G = H - TS (H -ve, S 0)
 G for the reaction is negative

Chelate Formation: Major Factors

[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en)

[Ni(en)3]2+ + 6NH3

 en and NH3 have similar N-donor environment

 but en is bidentate and chelating ligand
 rxn proceeds towards right, G negative
 G = H - TS ve S ++ve)
(H -ve,

 rxn proceeds due to entropy gain

 S ++ve is the major factor in chelate effect.

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H. W. 1:

Cd2+ + 4 NH3  [Cd(NH3)4]2+ Cd2+ + 4 MeNH2  [Cd(MeNH2)4]2+

Cd2+ + 2 en  [Cd(en)2]2+

Ligands log 

4 NH3 7.44

4 MeNH2 6.52

2 en 10.62

Chelate Effect : Data & understanding

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H.W. 2: How can you justify the chelate formation is

linked with entropy Gain?
Reaction of ammonia and en with Cu2+

[Cu(H2O)6]2+ + 2NH3  [Cu(NH3)2(H2O)2]2+ + 2 H2O

Log 2 = 7.7

[Cu(H2O)6]2+ + en  [Cu(en)(H2O)4]2+ + 2 H2O

Log K1 = 10.6

Kinetic stability Inert and labile complexes

The term inert and labile are relative

“A g
good rule of thumb is that those complexes
p that
o
react completely within 1 min at 25 should be
considered labile and those that take longer should be
considered inert.”

Thermodynamically stable complexes can be labile or inert

[Hg(CN)4]2- Kf= 1042 thermodynamically stable

[Hg(CN)4]2- + 4 14CN- = [Hg(14CN)4]2- + CN-

Very fast reaction Labile

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Chelating agents:

(1) Used to remove unwanted metal ions in water.

(2) Selective removal of Hg2+ and Pb2+ from body when poisoned.

(3) Prevent blood clots.

(4) Solubilize iron in plant fertilizer.

Important Chelating Ligands

2,3-dimercapto-1-propanesulfonic acid
sodium (DMPS)

Mn+

DMPS is a effective chelator with two groups thiols - for mercury, lead,
tin, arsenic, silver and cadmium.

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SH O

HO
OH

O SH Zn
As
(R,S)-2,3-dimercaptosuccinic acid D-Penicillamine Hg
Au
As, Cu, Pb, Hg Pb

SH S
M+
As
M Hg
OH Au
HS OH S Pb

Dimercaprol

Important Chelating Ligands

O EDTA O

*O C CH2 CH2 C O*
*
N *
CH2 CH2 N
*O C CH2 CH2 C O*

O O

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EDTA: another view

Ca2+
Anticoagulant

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