Bonding in coordination compounds
Nobel prize 1913
• Alfred Werner
• VBT
• Crystal Field Theory (CFT)
• Modified CFT, known as
Ligand Field Theory
• MOT
How & Why?
Valance Bond Model
Ligand = Lewis base
Metal = Lewis acid
s, p and d orbitals give hybrid orbitals with specific geometries
Number and type of M-L hybrid orbitals determines geometry of the complex
Octahedral Complex
e.g. [Cr(NH3)6]3+
Tetrahedral e.g. [Zn(OH)4]2- Square Planar e.g. [Ni(CN)4]2-
Limitations of VB theory
Can not account for colour of complexes
May predict magnetism wrongly
Can not account for spectrochemical series
Crystal Field Model
A purely ionic model for transition metal complexes.
Ligands are considered as point charge.
Predicts the pattern of splitting of d-orbitals.
Used to rationalize spectroscopic and magnetic
properties.
d-orbitals: look attentively along the axis
Octahedral Field
• 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.
In Octahedral Field
dyz
dz 2
dxz
dx2-
y2 dxy
In Tetrahedral 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
BEYOND d3
• In weak field: O P, => t2g3eg1
• In strong field O P, => t2g4
• P - paring energy
Magnitude of
Oxidation state of the metal ion
[Ru(H2O)6]2+ 19800 cm-1
[Ru(H2O)6]3+ 28600 cm-1
Nature of the metal ion
3d<4d<5d
Number and geometry of the ligand
t< o
Nature of the ligand
I-<S2-<SCN-<Cl-<NO3-<N3-<F-<OH-<C2O42-<H2O<…..CN-<CO
Ground-state Electronic Configuration,
Magnetic Properties and Colour
Ground-state Electronic Configuration,
Magnetic Properties and Colour
[Mn(H2O)6]3+
Weak Field Complex
the total spin is 4 ½ = 2
High Spin Complex
[Mn(CN)6]3-
Strong field Complex
total spin is 2 ½ = 1
Low Spin Complex
Ground-state Electronic Configuration,
Magnetic Properties and Colour
d5 ions, Oh field eg High Spin
+ 0.6 oct
CFSE = 0
- 0.4 oct
t2g 5 u.p.e-
eg Low Spin
+ 0.6 oct CFSE =
5 x - 0.4 oct + 2P
- 0.4 oct = - 2.0 oct + 2P
t2g
1 u.p.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
NC CN
- 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 oct, what spin state is it in?
C.N. = 6 Oh Co(II) d7 h.s. l.s.
OH 2 2+ eg eg
OH 2 + 0.6 oct
H 2O
Co
H 2O OH 2 - 0.4 oct
t2g t2g
OH 2
CFSE = (5 x - 0.4 oct) CFSE = (6 x - 0.4 oct)
+ (2 x 0.6 oct) = - 0.8 oct + (0.6 oct) + P= - 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/4me = 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
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
Gouy balance to
measure the magnetic
susceptibilities
The origin of the color of the transition
metal compounds
E2
E h
E1
E = E2 – E1 = h
Ligands influence O, therefore the colour
The colour can change depending on a number of factors
e.g.
1. Metal charge
2. Ligand strength
The optical absorption spectrum of [Ti(H2O)6]3+
Assigned transition:
eg t2g
This corresponds to
the energy gap
O = 243 kJ mol-1
• Spectrochemical Series: An order of ligand
field strength based on experiment:
Weak Field I- Br- S2- SCN- Cl-
NO3- F- C2O42- H2O NCS-
CH3CN 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)
[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 overlap between 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
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
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]
O C M
orbital serves as a very weak donor to a metal atom
O C M O C M O C M
CO-M sigma bond M to CO pi backbonding CO to M pi bonding
(rare)
