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Bonding in coordination compounds

• Introduction….
Nobel prize 1913
• Alfred Werner - 1893
• VBT
• Crystal Field Theory (CFT)
• Modified CFT, known as
Ligand Field Theory
• MOT

[Fe(H2O)6]3+ [Ni(H2O)6]2+ [Zn(H2O)6]2+

[Co(H2O)6]2+ [Cu(H2O)6]2+

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Gemstone owe their color from

trace transition-metal ions
• Corundum mineral, Al2O3: Colorless
• Cr  Al : Ruby
• Mn  Al: Amethyst
• Fe  Al: Topaz
• Ti &Co  Al: Sapphire

• Beryl mineral, Be3 Al 2Si6O18: Colorless

• Cr  Al : Emerald
• Fe  Al : Aquamarine

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How & Why?

Valance Bond Theory

Basic Principle

A covalent bond forms when the orbtials of two

atoms overlap and are occupied by a pair of
electrons that have the highest probability of
being located between the nuclei.
Linus Carl Pauling
(1901-1994)
Nobel prizes: 1954, 1962

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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+

Tetrahedral e.g. [Zn(OH)4]2- Square Planar e.g. [Ni(CN)4]2-

Limitations of VB theory
Cannot account for colour of complexes
May predict magnetism wrongly
Cannot account for spectrochemical series

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Crystal Field Theory

400 500 600 800

•The
relationship
between colors
and complex
metal ions

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

Linear combination of
dz2-dx2 and dz2-dy2

d2z2-x2-y2

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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d x -y d z2
2 2

Do
or
10 Dq

dxy dyz dxz

d x -y d z2
2 2

+ 0.6
Do
or
+ 6 Dq

- 0.4
Do
or
- 4 Dq
dxy dyz dxz

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In Octahedral Field
dyz

dz2

dxz

dx 2 -
y2 dxy

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In Tetrahedral Field

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Distortion

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Tetragonal Complexes
The elongation
along the z axis causes
the d orbitals with
density along the axis
to drop in energy. As a
result, the dxz and dyz
orbitals lower in
energy.

Tetragonal Complexes
The compression
along the x and y axis
causes orbitals with
density along these
axes to increase in
energy.
.

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Tetragonal Complexes
For complexes with
1-3 electrons in the eg
set of orbitals, this type
of tetragonal distortion
may lower the energy
of the complex.

Square Planar Complexes

For complexes with 2
electrons in the eg set of
orbitals, a d8
configuration, a severe
distortion may occur,
resulting in a 4-coordinate
square planar shape, with
the ligands along the z axis
no longer bonded to the
metal.

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Square Planar Complexes

Square planar
complexes are quite
common for the d8 metals
in the 4th and 5th periods:
Rh(I), IR(I), Pt(II), Pd(II)
and Au(III). The lower
transition metals have
large ligand field
stabalization energies,
favoring four-coordinate
complexes.

Square Planar Complexes

Square planar
complexes are rare for the
3rd period metals. Ni(II)
generally forms tetrahedral
complexes. Only with
very strong ligands such as
CN-, is square planar
geometry seen with Ni(II).

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Square Planar Complexes

The value of ∆sp for a
given metal, ligands and
bond length is
approximately 1.3(∆o).

The Jahn-Teller Effect

If the ground electronic configuration of a

non-linear complex is orbitally degenerate,
the complex will distort so as to remove the
degeneracy and achieve a lower energy.

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The Jahn-Teller Effect

The Jahn-Teller effect predicts which
structures will distort. It does not predict
the nature or extent of the distortion. The
effect is most often seen when the orbital
degneracy is in the orbitals that point
directly towards the ligands.

The Jahn-Teller Effect

In octahedral complexes, the effect is
most pronounced in high spin d4, low spin
d7 and d9 configurations, as the degeneracy
occurs in the eg set of orbitals.
d4 d7 d9
eg

t2g

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The Jahn-Teller Effect

The strength of the Jahn-Teller effect is
tabulated below: (w=weak, s=strong)
# e- 1 2 3 4 5 6 7 8 9 10
High
* * * s - w w * * *
spin
Low
w w - w w - s - s -
spin

*There is only 1 possible ground state configuration.

- No Jahn-Teller distortion is expected.

d9 system

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d7 system (low spin)

d4 system (high spin)

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Magnitude of D

Oxidation state of the metal ion

[Ru(H2O)6]2+ 19800 cm-1
[Ru(H2O)6]3+ 28600 cm-1

Number of ligands and geometry

Dt< Do Dt= 4/9Do

Nature of the ligand

I-<S2-<SCN-<Cl-<NO3-<N3-<F-<OH-<C2O42-<H2O<…..CN-<CO

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)DO
DO = 10 Dq
BEYOND d3
• In weak field: DO  P, => t2g3eg1
• In strong field DO  P, => t2g4
• P - paring energy

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Hydration Enthalpy of M2+ ions (H2O is weak field ligand, the

complexes are high spin).

M2+(g) + 6 H2O(l) = [M(O2H)6]2+(aq)

Plotting the enthalpy across the first transition series

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Ground-state Electronic Configuration,

Magnetic Properties and Colour

When the 4th electron is assigned it will either go into the higher
energy eg orbital at an energy cost of Do 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 < Do P > Do
Coulombic repulsion energy and exchange energy

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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

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.

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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 Doct
NC CN
- 0.4 Doct
CN t2g
t2g

CFSE = 5 x - 0.4 Doct + 2P = - 2.0 Doct + 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.

OH2 2+ eg eg
OH 2 + 0.6 Doct
H 2O
Co
H 2O OH2 - 0.4 Doct
t2g t2g
OH2

CFSE = (5 x - 0.4 Doct) CFSE = (6 x - 0.4 Doct)

+ (2 x 0.6 Doct) +2P = - 0.8 Doct+2P + (0.6 Doct) + 3P= - 1.8 Doct + P

The origin of the color of the transition

metal compounds
E2

DE h

E1

DE = E2 – E1 = h
Ligands influence DO, 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

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

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

490 nm

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absorbed observed
color color

• 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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Spectrochemical Series
Or more simply :
X<O<N<C

[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, D increases and the
color of the complex changes from green to yellow.

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[Fe(H2O)6]3+ [Ni(H2O)6]2+ [Zn(H2O)6]2+

[Co(H2O)6]2+ [Cu(H2O)6]2+

Intensity of color?
Selection rule

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n = no. of unpaired electrons

 = {n(n+2)}1/2 B
 = 2{S(S+1)}1/2
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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• 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 Dt  DO.

Determination Magnetic Properties

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Gouy balance to
measure the magnetic
susceptibilities

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

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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.

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]

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)

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[Co(H2O)6]2+ vs [Co(NH3)6]2+ pink/orange

[Co(H2O)6]2+ vs [CoCl4]2- pink/intense blue

[FeF6]3- vs [CoF6]3- colorless/color

Spin only Mag. Moment

[Fe(CN)6]3-
Td [FeCl4]2-
[Cr(NH3)6]2+

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