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Crystal Field Theory

Crystal field theory (CFT) and ligand field theory (LFT) were developed to explain the colors and magnetic properties of coordination compounds. CFT considers ligands as point charges and predicts the splitting of d-orbitals into higher-energy eg and lower-energy t2g sets. The magnitude of splitting (Δo) depends on factors like the metal's oxidation state and nature of ligands. Complexes are classified as high-spin or low-spin based on whether the 4th electron occupies eg or pairs with t2g. Color and magnetism can then be explained. Later, LFT improved on CFT by including orbital overlap to better describe complexes with metals in low oxidation states, where ligands like CO can

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532 views

Crystal Field Theory

Crystal field theory (CFT) and ligand field theory (LFT) were developed to explain the colors and magnetic properties of coordination compounds. CFT considers ligands as point charges and predicts the splitting of d-orbitals into higher-energy eg and lower-energy t2g sets. The magnitude of splitting (Δo) depends on factors like the metal's oxidation state and nature of ligands. Complexes are classified as high-spin or low-spin based on whether the 4th electron occupies eg or pairs with t2g. Color and magnetism can then be explained. Later, LFT improved on CFT by including orbital overlap to better describe complexes with metals in low oxidation states, where ligands like CO can

Uploaded by

Rahmi Hayatunnufus
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPT, PDF, TXT or read online on Scribd
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Bonding in coordination compounds

Nobel prize 1913

Alfred Werner - 1893


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

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.

LinusCarlPauling
(19011994)
Nobelprizes:1954,1962

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

Crystal Field Theory


400

500

600

The
relationship
between
colors and
complex metal
ions

800

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


Linear combination of
dz2-dx2 and dz2-dy2
d2z2-x2-y2

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

yz

xz

z2

x2-y2
d

xy

In Tetrahedral Field

Magnitude of
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


t< o

t= 4/9 o

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) O
O = 10 Dq

BEYOND d3
In weak field: O P, => t2g3eg1
In strong field O P, => t2g4
P - paring energy

Ground-state Electronic Configuration,


Magnetic Properties and Colour

Whenthe4thelectronisassigneditwilleithergointothehigher
energyegorbitalatanenergycostofoorbepairedatanenergy
costofP,thepairingenergy.
d4
Strongfield=
Lowspin
(2unpaired)

P < o
P > o
Coulombicrepulsionenergyandexchangeenergy

Weakfield=
Highspin
(4unpaired)

Ground-state Electronic Configuration,


Magnetic Properties and Colour
[Mn(H2O)6]3+
Weak Field Complex
the total spin is 4 = 2
High Spin Complex
[Mn(CN)6]3Strong field Complex
total spin is 2 = 1
Low Spin Complex

Placingelectronsindorbitals
d5

1u.e.

5u.e.

d6

0u.e.

4u.e.

d8

2u.e.

2u.e.

d7

1u.e.

3u.e.

d9

1u.e.

1u.e.

d10

0u.e.

0u.e.

What is the CFSE of [Fe(CN)6]3-?


C.N. = 6 Oh

Fe(III) d5
3-

CN
NC

Fe

NC

h.s.

l.s.
eg

CN

CN- = s.f.l.
eg
+ 0.6 oct

CN

CN

- 0.4 oct

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

OH2
H 2O

Co

H 2O
OH2

2+

h.s.

l.s.
eg

eg

+ 0.6 oct

OH2
OH2

t2g

t2g

- 0.4 oct

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/4me = 9.274 10-24 J T-1
Since each unpaired electron has a spin ,
S = ()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

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

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(H 2O)6]3+


Assigned transition:
eg

t2g

This corresponds to
the energy gap
O = 243 kJ mol-1

absorbed
color

observed
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

H2 N

NH2

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 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

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]

orbital serves as a very weak donor to a metal atom

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