BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 19
22 Feb 2019
AY 2018-19, Sem-II
CFT
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Lecture 18- Summary
Topics discussed in last class
 Isomerism
 Shapes of d orbitals
 Crystal field theory – Assumptions and general
descriptions
 d-orbital splitting octahedral complexes
 d-orbital splitting in tetrahedral complex
 Spectrochemical series

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Dependence of o
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., M belongs to I, II, or III row

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Bonding in Coordination Complexes
Crystal Field Theory (CFT) – Approach of Ligands (Octahedral field)

Lobes are directed Lobes are directed in

towards ligands between ligands
greater electrostatic repulsion = higher potential energy

MORE Destabilized LESS Destabilized

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Crystal Field Theory
Octahedral crystal field
_ _
d orbital energy levels dz2 dx2- y2
oct

E _ _ _
dxy dxz dyz

_____
Under ligand field ONLY
d-orbitals
isolated Metal ion and the nature of the ligand
metal ion determines oct

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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 
IMPORTANT POINTS
 Based on experimental data
 There is no apparent 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 can be as
Halide donors < O donors < N donors < C donors
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Spectrochemical series
Within halide donors for o: I- < Br- < Cl- < F-: Explanation
Consider in terms of electrostatic
repulsions. F- is of small size and
hence more closer bonding and
more repulsion (higher o)

Explain the order PPh3 < CN- < CO

• o for CN- is almost double that of I- ; This can
not be explained by CFT. Covalent bonding of 
and  types of bonding is to be included
 (pi) back bonding
•CO, phosphines are neutral ligands and still from metal t2g 
produce the maximum splitting of d orbitals vacant ligand-orbital
which implies electrostatic-point charge model
is not sufficient
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Nature of metal cation
(i) Different charges on the cation of the same metal:
Δo for [Fe(H2O)6]2+= 10,400 cm-1
Δo for [Fe(H2O)6]3+= 13,700 cm-1
For the same metal, the metal cation with a higher oxidation state
has a larger value of Δo than that with lower oxidation state.
Table: comparison of 0 for different M[(H2O)6]n+ complexes
Oxdn
M Ti V Cr Mn Fe Co Ni Cu
State
e’
+II d2 d3 d4 d5 d6 d7 d8 d9
config

o, cm-1 - 12600 13900 7800 10400 9300 8500 12600

e’
+III d1 d2 d3 d4 d5 d6 d7 d8
config

o, cm-1 20300 18900 17830 21000 13700 18600 - -

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Nature of metal cation
(ii) Same d-electrons: Different charges on the cation of
different metal with same number of d-electron : Two different
cations with the same number of d-electrons but with different
charge (metals within a same period)
Δo for [V(H2O)6]2+= 12,600 cm-1
Δo for [Cr(H2O)6]3+= 17,830 cm-1
The cation with the higher charge will have bigger o

(iii) Same charge on the cation of different metal but different

d- electrons (metals within a same period): (Exceptional, trend
is not followed properly, many factors are responsible)
Δo for [Co(H2O)6]2+= 9300 cm-1
Δo for [Ni(H2O)6]2+= 8500 cm-1

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Nature of metal cation
(iv) Size of the metal ion
Variation down any group
Δo for [Cr(NH3)6]3+= 24,800 cm-1
Δo for [Ru(NH3)6]3+= 34,000 cm-1
Δo for [Ir(NH3)6]3+= 41,000 cm-1
The o of metal cations generally increase by almost 30 %,
moving down the group
- Larger the d orbital size it is easier to split, larger o
- 5d orbitals split larger than 4d orbitals, which in turn may be
larger than 3d, and so on

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Electronic configuration of
Octahedral (Oh) complexes
Expected orbital filling tendencies for electrons:
 Occupy lowest energy vacant orbitals first
 Occupy a set of equal energy orbitals one at a time (Hund’s
rule), which minimizes repulsions

d orbital occupancy depends on Δ and pairing energy, P

• If Δ > P (Δ is large; strong field ligand)
 e-’s pair up in lower energy d-orbitals first
• If Δ < P (Δ is small; weak field ligand)
 e-’s spread out among all d-orbitals before any pair up
P is a constant for each metal ion

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d orbital occupancy
d1 d2

d4 d4

high spin,  < P low spin,  > P

Configuration with higher number of unpaired electrons is called

HIGH Spin or Spin-free, one with lowest number of unpaired spins is
called LOW-spin or spin-paired configuration
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Tetrahedral complexes
_
_
_ 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
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Tetrahedral complexes
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 in the interaction energy

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), there are a few exceptions though

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Octahedral vs. tetrahedral
Octahedral
____ e
Tetrahedral g

____
t2 __ 0.6 ΔO

E 0.4 Δt __
__
_
Bari center -0.4 ΔO
-0.6 Δt
(considering same) ____
___
_ __ t2g
e
So for the same ligand and same metal ion
t = (4/9)o (approximately)

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Example - d6 configuration
Weak Strong

eg t2g6eg0
eg

E o t2g4eg2 E o Octahedron

t2g t2g

t2 t2
e3t23
E e3t23 E
Tetrahedron
e e

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Crystal Field Stabilization Energy
In the d1 system (t2g1eg0), one electron is 0.4 o below Bari Centre.
OR this electron is stabilized in an octahedral field w.r.t.
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

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CFSE for a d-electron configuration
eg
Similarly, V3+ = d2 = t2g2 So CFSE = - 0.8 o
E

t2g

Cr3+ = d3 = t2g3 CFSE = - 1.2 o eg

E

t2g

Due to Hund’s rule of maximum multiplicity the electrons are going to

different orbitals

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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

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CFSE of d4 configuration
Case I Case II

eg eg
E o E ’o
t2g t2g

o>>’o
Case I Case II
P << o o’ << P
Low spin complex; high spin Complex;
Spin paired complex; spin free complex;
Strong ligands Weak ligands

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CFSE for Octahedral complexes
Weak Field Ligand Strong Field Ligand
dn Configuration Unpaired CFSE Configuration Unpaired CFSE
electrons (in o) electrons (in 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

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Tetrahedral complexes

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

strong or weak field ligands

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Uses of CFSE values
Stabilization of oxidation state

(i) [Co(H2O)6]3+ : 3d6 system, t2g4eg2, CFSE: -0.4 ΔO

(ii) [Co(H2O)6]2+ : 3d7 system, t2g5eg2, CFSE: -0.8 ΔO

(iii) [Co(NH3)6]3+ (CFSE: -2.4 ΔO) and [Co(NH3)6]2+ (CFSE: -1.8 ΔO)

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Crystal Field Theory: lattice energy
CRYSTAL FIELD THEORY in explaining variation of Lattice Energy for
transition metal chlorides (1st row transition metals)

In these solids, the coordination

number of these metals is 6, hence
analogous to Oh complexes

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

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Crystal Field Theory: Hydration energy
CRYSTAL FIELD THEORY in explaining variation of Hydration Energy
of M2+ ions of first row transition elements

M2+(g) + H2O(excess)  [M(H2O)6]2+ H= -ve

Zero CFSE cases are d0, d5
(weak) and d10 configurations
i.e. Ca2+, Mn2+, and Zn2+
All other ions have additional
stability which is CFSE –
Values obtained are in
agreement those from
spectroscopy
Analogy holds good for M3+
ions also 25 BITS Pilani, Pilani Campus
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

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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.

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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

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Discussed topics……

 Factors affecting the magnitude of ΔO

Crystal field stabilization energy in Octahedral geometry
 CFSE calculation of tetrahedral complexes
 Uses of CFSE: stabilization of oxidation state, lattice energy,
hydration energy, and ionic radii

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