Bonding in coordination compounds

Nobel prize 1913

• Alfred Werner
• VBT
• Crystal Field Theory (CFT)
• Modified CFT, known as
Ligand Field Theory
• MOT

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How & Why?

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 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+

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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

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 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.

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d-orbitals: look attentively along the axis

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Octahedral Field

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• 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.
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In Octahedral Field
dyz

dz 2

dxz

dx2-
y2 dxy
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In Tetrahedral Field

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 Crystal Field Stabilization Energy SE)
• 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
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 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
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Ground-state Electronic Configuration,
Magnetic Properties and Colour

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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
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 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-
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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.

OH2 2+ eg eg
OH2 + 0.6 ∆oct
H2O
Co
H2O OH2 - 0.4 ∆oct
t2g t2g
OH2

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 +20
P
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• The magnetic moment µ of a complex with total
spin quantum number S is:
• µ = 2{S(S+1)}1/2 µB (µB is the Bohr magneton)
• µB = eh/4πme = 9.274 ×10-24 J T-1
• Since each unpaired electron has a spin ½,
• S = (½)n, where n = no. of unpaired electrons
• µ = {n(n+2)}1/2 µB
• 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.
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 n = no. of unpaired electrons
µ = {n(n+2)}1/2 µB
Ion n S µ/µB 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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Gouy balance to
measure the magnetic
susceptibilities

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 The origin of the color of the transition
metal compounds
E2

∆E hν

E1

∆E = E2 – E1 = hν
Ligands influence ∆O, therefore the colour

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The colour can change depending on a number of factors
e.g.
1. Metal charge
2. Ligand strength

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

Assigned transition:
t2g eg
This corresponds to
the energy gap
∆O = 243 kJ mol-1
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• 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

H2N 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.
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 The Jahn-Teller effect

Jahn-Teller theorem:
“A degenerate system will undergo distortion to eliminate degeneracy”

Molecules will distort to eliminate the degeneracy

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 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

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 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.

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Stabilizing Low Oxidation State: CO Can Do the Job

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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]
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 O C M

σ 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) 40
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