What is a Transition Metal?

Color of transition metal complexes

Sapphire: Al2O3 with and Impurity
titanium and iron impurities are
present together, and in the
correct valence states, the result is a
deep-blue color. Fe2+ and Ti4+ ions
are substituted for Al3+

Ruby : Al2O3 With

Impurity of Chromium

Emerald is a gemstone and a variety of the mineral beryl (Be3Al2(SiO3)6)

colored green by trace amounts of chromium and sometimes vanadium
Naturally Occurring Coordination Compounds
Crystal Field Theory

Dr. C. Haldar
Department of Chemistry, IIT (ISM)
1. A purely ionic model for transition metal complexes. In its simplest treatment CFT
does not consider covalent bonding in complexes.
2. Ligands are considered as point charge.
3. The CFT does not provide for electrons to enter the metal orbitals, i.e. it does not
consider any orbital overlap.
4. Predicts the pattern of splitting of d-orbitals.
5. Used to rationalize spectroscopic and magnetic properties.

Octahedral complex (Oh) Tetrahedral complex (Td) Square planer complex (Sp)
d-orbitals: look attentively along the axis
• We assume an octahedral array of negative charges placed
around the metal ion (which is positive).
• The ligand and orbitals lie on the same axes as negative
charges.
– Therefore, there is a large, unfavorable interaction between
ligand (-) and these orbitals.
– These orbitals form the degenerate high energy pair of
energy levels.
• The dxy, dyz, and dxz orbitals bisect the negative charges.
– Therefore, there is a smaller repulsion between ligand and
metal for these orbitals.
– These orbitals form the degenerate low energy set of energy
levels.
Octahedral Field
In Octahedral Field

dyz

dz2

dxz

dx2-y2

dxy
Distortions of Octahedral Complexes
Distortions of Octahedral Complexes: Jahn-Teller effect
‘Any non-linear molecule having an orbitally degenerate electronic
configuration is unstable, and the system undergo distortion to remove
the degeneracy.’

Examples: [Cu(NH3)6]2+ - d9, d7(LS), d4(HS), d1, d2, d5(LS), d6(HS)

In Tetrahedral Field
 Since

t< o

t= 0.45 o
For the same metal and ligands and the same
internuclear distances

Crystal field splitting favors the formation of octahedral complexes

 Factors influencing the Magnitude of  for Octahedral complexes

1. The nature of metal cation:

i) Oxidation state of the metal ion
[Ru(H2O)6]3+ 28600 cm-1
[Ru(H2O)6]2+ 19800 cm-1
ii) Different charges on the cation of different metals
[V(H2O)6]2+ 12400 cm-1 3d3
[Cr(H2O)6]3+ 17400 cm-1 3d3
iii) Same charges on the cation but the number of d- electrons is different
[Co(H2O)6]2+ 9300 cm-1 3d7
[Ni(H2O)6]2+ 8500 cm-1 3d8
iv) Quantum number (n) of the d- orbitals of the central metal ion.
[Co(NH3)6]3+ 23000 cm-1 3d6
[Rh(NH3)6]3+ 34000 cm-1 4d6
[Ir(NH3)6]3+ 41000 cm-1 5d6

o increases about 30% to 50% from 3dn to 4dn. And by about

same amount again from 4dn to 5dn.
 Strong and weak ligands: Spectrochemical Series

Weak Field I-  Br- S2- SCN- Cl- NO3- F-  C2O42-

H2O NCS- CH3CN NH3 en  bipy phen NO2-
 PPh3 CN- CO Strong Field
 Crystal Field Splitting Energy (CFSE)
• In Octahedral field, configuration is: t2gx egy
• Net energy of the configuration relative to the average energy
of the orbitals is:
= (-0.4x + 0.6y)O
O = 10 Dq

BEYOND d3
• In weak field: O  P, => t2g3eg1
• In strong field O  P, => t2g4
• P - pairing energy
Ground-state Electronic Configuration,
Magnetic Properties and Colour

d2 Ti2+, V3+

d3 Cr3+, Mn4+,V2+
When the 4th electron is assigned it will either go into the higher
energy eg orbital at an energy cost of o or be paired at an energy cost
of P, the pairing energy.

d4

Strong field = Weak field =

Low spin High spin
(2 unpaired) (4 unpaired)

P < o P > o
Coulombic repulsion energy and exchange energy
Ground-state Electronic Configuration,
Magnetic Properties

[Mn(H2O)6]3+
Weak Field Complex
the total spin (S) is 4  ½ = 2
High Spin Complex

Weak field d4

[Mn(CN)6]3-
Strong field Complex
total spin (S) is 2  ½ = 1
Low Spin Complex

Strong field d4
 Placing electrons in d orbitals

d5 d6 d7

1 u.e. 5 u.e. 0 u.e. 4 u.e. 1 u.e. 3 u.e.

d8 d9 d10

2 u.e. 2 u.e. 1 u.e. 1 u.e. 0 u.e. 0 u.e.

What is the CFSE of [Fe(CN)6]3-? CN- = S.F.L.
C.N. = 6  Oh Fe(III)  d5 H.S. L.S.
CN 3-
eg eg
CN
NC
Fe + 0.6 oct
CN
NC
- 0.4 oct
CN
t2g t2g

CFSE = 5 x - 0.4 oct + 2P = - 2.0 oct + 2P

If the CFSE of [Co(H2O)6]2+ is -0.8 Doct, what spin state is it in?

C.N. = 6  Oh Co(II)  d7 H.S. L.S.

2+ eg eg
OH2
+ 0.6 oct
OH2
H 2O
Co - 0.4 oct
H 2O
OH2
t2g t2g
OH2

CFSE = (5 x - 0.4 oct) CFSE = (6 x - 0.4 oct)

+ (2 x 0.6 oct) +2P = - 0.8 oct+2P + (0.6 oct) + 3P= - 1.8 oct + P
• 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
• In d4, d5, d6, and d7 octahedral complexes, magnetic
measurements can very easily predict weak versus strong field.
• Tetrahedral complexes - only high spin complexes result,
for t  O.
 n = no. of unpaired electrons
 = {n(n+2)}1/2 B
Ion n S /B Experimental
Calculated

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
Mn2+ 5 5/2 5.92 5.9 - 6.3

Similar Calculation can be done

for Low-spin Complex
 The origin of the color of the transition
metal compounds
E2

E h

E1

E = E2 – E1 = h

Ligands influence O, therefore the colour

absorbed observed
color color
The colour can change depending on a number of factors
e.g.
1. Metal charge
2. Ligand strength
 [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.
 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
 Ligand Field Theory: Concepts
p-orbitals
 Ligand Orbitals(LGO)are
obtained by Linear
Combination of Atomic
Orbitals (LCAO)
 LGOs overlap with
symmetry related Metal
Orbitals

M L
MO diagram of an Octahedral complex
 Metals in Low Oxidation States

• In low oxidation states, the electron density on the metal ion is very high.
• To stabilize low oxidation states, we require ligands, which can simultaneously bind
the metal center and also withdraw electron density from it.
Stabilizing Low Oxidation State: CO Can Do the Job
*

π*

nb

nb

*


MO of π-complex
Stabilizing Low Oxidation State: CO Can Do the Job

Ni(CO)4], [Fe(CO)5], [Cr(CO)6], [Mn2(CO)10],

[Co2(CO)8], Na2[Fe(CO)4], Na[Mn(CO)5]