INTRODUCTION

• CFT WAS DEVELOPED BY H.BETHE AND V.BLECK.

• THIS THEORY GIVES A MUCH MORE SATISFACTORY EXPLANATION FOR BONDING AND THE PROPERTIES OF
COORDINATION COMPLEXES.
• THE VALENCE BOND THEORY CONSIDERS BONDING BETWEEN THE METAL ION AND LIGAND PURELY
COVALENT, WHEREAS THE CRYSTAL FIELD THEORY CONSIDERS THE METAL LIGAND BOND TO BE IONIC
ARISING FROM ELECTROSTATIC INTERACTIONS BETWEEN THE METAL ION AND THE LIGANDS.
• THE LIGANDS ARE TREATED AS POINT CHARGES.
THE SHAPE OF 5 D-ORBITALS
• In the case of free metal ion, all the five d
orbitals have the same energy.
• These orbitals having same energies are
called degenerate orbitals.
• This means that an electron can occupy any
one of these five d orbitals with equal ease
• However, on the approach of ligands,the
orbitals electrons will be repelled by the lone
pairs of the ligand.
• The repulsion will raise the energy of d
orbitals. After approaching ligands to central
Metal/ ion the energy of these orbitals will
increase.
OCTAHEDRAL SPLITTING OF D ORBITAL
• The conversion of 5 degenerate d orbitals of
the metal ion into different sets of orbitals
having different energies in presence of
electrical field of ligand is called crystal
field splitting.
• In the case of octahedral complexes, the five
d orbitals split up into two sets.
• One sets consists of two orbitals d x2-dy2
• and dz2 of higher energy and other sets
consists of three orbitals dxy, dyz,dzx of lower
energy.
SPECTROSCOPIC TERMS

• In octahedral field of splitting the two d orbitals dz2 and dx2-dy2are called eg
orbitals . Three d orbitals dxy, dyz,dzx are called t 2g orbitals
BARYCENTRE RULE

• THE CRYSTAL FIELD SPLITTING EXSIST IN SUCH A WAY THE AVERAGE ENERGY OF D ORBITALS DOES NOT
CHANGE . THIS IS BARY CENTRE RULE WHICH IS SIMILAR TO CENTRE OF GRAVITY . THIS MEANS THAT THE
3 ORBITALS LIE AT ENERGY THAT IS 2/5 ∆O (0.4 ∆O) BELOW THE AVERAGE D ORBITAL ENERGY AND 2 D
ORBITALS LIE AT ENERGY 3/5 ∆O ABOVE THE AVERAGE ENERGY.
STRONG V/S WEAK LIGAND
• STRONG FIELD LIGANDS CONTAIN ATOMS IN • WEAK FIELD LIGANDS CONTAIN ATOMS FROM
THE HIGHER ENERGY STATE. BOTH THE LOWEST ENERGY GROUND STATE
AND HIGHEST ENERGY EXCITED STATE,
• STRONG FIELD LIGANDS ARE WEAKER IN • WEAK FIELD LIGANDS ARE STRONGER IN
TERMS OF THEIR ABILITY TO FORM TERMS OF THEIR ABILITY TO FORM
INTERMOLECULAR INTERACTIONS INTERMOLECULAR INTERACTIONS
• THE STRONG FIELD CAN ACT AS LEWIS ACIDS • WEAK FIELD LIGANDS CAN ACT AS LEWIS ACIDS
ONLY IN IONIC SPECIES. IN BOTH IONIC AND RADICAL SPECIES
SPECTROCHEMICAL SERIES
 FILLING OF ELECTRONS
• The single d electron occupies one of the lower energy t2g orbitals. In d2 and d3
coordination entities, the d electrons occupy the t2g orbitals singly in
accordance with Hund’s rule.
• For d 4 ions, two possible patterns of electron distribution arise:
• (i) the fourth electron could either enter the t 2g level and pair with an existing
electron, or
• (ii) it could avoid paying the price of the pairing energy by occupying the eg level.
 FILLING OF D ORBITAL
• The possibilities occurs, depends on the relative magnitude of the crystal field
splitting, ∆o and the pairing energy, P (P represents the energy required for
electron pairing in a single orbital). The two options are:
(i) If ∆o < P, the fourth electron enters one of the eg orbitals giving the
configuration t2g3 eg1. Ligands for which ∆o < P are known as weak field ligands and
form high spin complexes.
(ii) If ∆o > P, it becomes more energetically favorable for the fourth electron to
occupy a t2g orbital with configuration t2g4 eg0. Ligands which produce this effect
are known as strong field ligands and form low spin complexes.
• Calculations show that d4 to d7 coordination entities are more stable for strong
field as compared to weak field cases
TETRAHEDRAL SPLITTING OF D ORBITALS
• The conversion of 5 degenerate d orbitals of
the metal ion into different sets of orbitals
having different energies in presence of
electrical field of ligand is called crystal field
splitting.
• In the case of octahedral complexes the five d
orbitals split up into two sets.
• One sets consists of two orbitals d z2 and dx2-
dy2 of lower energy and other sets consists of
three orbitals dxy, dyz,dzx of higher energy
TETRAHEDRAL COORDINATION ENTITY
• In tetrahedral coordination entity formation, the d orbital splitting is inverted
and is smaller as compared to the octahedral field splitting.
• For the same metal, the same ligands and metal-ligand distances, it can be
shown that ∆t = (4/9) ∆o .
• Consequently, the orbital splitting energies are not sufficiently large for
forcing pairing and, therefore, low spin configurations are rarely observed.
• The ‘g’ subscript is used for the octahedral and square planar complexes
which have Centre of symmetry. Since tetrahedral complexes lack symmetry,
‘g’ subscript is not used with energy levels.
OCTAHEDRAL & TETRAHEDRAL SPLITTING
• ARRANGEMENT OF LIGANDS: SIX LIGANDS ARE • ARRANGEMENT OF LIGANDS: FOUR LIGANDS ARE
ARRANGED AROUND THE CENTRAL METAL ION, ARRANGED AROUND THE CENTRAL METAL ION,
FORMING A TETRAHEDRON.
FORMING AN OCTAHEDRON.
• D-ORBITAL SPLITTING: THE D-ORBITALS SPLIT • D-ORBITAL SPLITTING: THE D-ORBITALS ALSO SPLIT
INTO TWO SETS, BUT THE ORDER IS REVERSED: E
INTO TWO SETS: T2G SET: LOWER IN ENERGY, SET: LOWER IN ENERGY, CONSISTING OF D X2 - DY2
CONSISTING OF DXY, DYZ,DZX ORBITALS. EGSET: AND DZ2
HIGHER IN ENERGY, CONSISTING DZ2 AND • ORBITALS. T2 SET: HIGHER IN ENERGY, CONSISTING
DX2-DY2ORBITALS. OF DXY, DYZ AND DZX ORBITALS.
OCTAHEDRAL & TETRAHEDRAL SPLITTING
• MAGNITUDE OF SPLITTING: THE SPLITTING ENERGY • MAGNITUDE OF SPLITTING: THE SPLITTING ENERGY
(ΔO) IS LARGER DUE TO STRONGER LIGAND-METAL (ΔT) IS SMALLER DUE TO WEAKER LIGAND-METAL
INTERACTIONS
INTERACTIONS. TYPICALLY, ∆T ≈ 4/9 ∆O.
• SPIN STATE: COMPLEXES CAN BE EITHER HIGH-SPIN • SPIN STATE: COMPLEXES ARE ALMOST ALWAYS
OR LOW-SPIN, DEPENDING ON THE LIGAND
STRENGTH AND THE PAIRING ENERGY OF THE HIGH-SPIN DUE TO THE SMALLER SPLITTING
ELECTRONS. ENERGY
• COLOR: COMPLEXES OFTEN EXHIBIT INTENSE • COLOR: COMPLEXES USUALLY HAVE WEAKER
COLORS DUE TO THE LARGER SPLITTING ENERGY,
COLORS DUE TO THE SMALLER SPLITTING ENERGY.
ALLOWING FOR D-D TRANSITIONS.
FACTORS DETERMINING THE MAGNITUDE
OF THE ORBITALS SPLITTING ENERGY
• 1) NATURE OF LIGAND THE ∆ VALUE DEPENDS UPON THE NATURE OF THE LIGAND. THE GREATER THE EASE
WITH WHICH THE LIGAND CAN APPROACH THE METAL ION AND INTERACT WITH IT, THE GREATER THE
EASE WITH WHICH THE LIGAND CAN APPROACH THE METAL ION AND INTERACT WITH IT, THE GREATER
WILL BE THE CRYSTAL FIELD SPLITTING ENERGY.THE LIGAND WHICH CAUSE ONLY SMALL ∆ VALUE ARE
CALLED WEAK FIELD LIGANDS WHILE THOSE WHO WHICH CAUSE A LARGE ∆ VALUE ARE CALLED
STRONG FIELD LIGANDS
FACTORS DETERMINING THE MAGNITUDE
OF THE ORBITALS SPLITTING ENERGY

• 2) OXIDATION STATE OF THE METAL ION.THE HIGHER THE IONIC CHARGE ON THE CENTRAL METAL ION. THE
GREATER THE VALUE OF ∆.
• 3) GEOMETRY OF THE COORDINATION ENTITY.THE ∆ VALUE FOR TETRAHEDRAL COORDINATION ENTITIES IS
ABOUT HALF THE ∆ VALUE FOR OCTAHEDRAL ENTITIES. ∆T = 4/9∆O
COLOR IN COORDINATION COMPOUNDS
• The color of the complex is complementary to that which is absorbed. The
complementary color is the color generated from the wavelength left over; if
green light is absorbed by the complex, it appears red
• . This is an octahedral complex where the single electron (Ti3+ is a 3d1 system)
in the metal d orbital is in the t2g level in the ground state of the complex. The
next higher state available for the electron is the empty eg level.
• If light corresponding to the energy of blue-green region is absorbed by the
complex, it would excite the electron from t2g level to the eg level (t2g1 eg0 or
t2g 0 eg 1 ). Consequently, the complex appears violet in color.
COLOR IN COORDINATION COMPOUNDS
• The crystal field theory attributes the color of the coordination compounds to
d-d transition of the electron.
• it is important to note that in the absence of ligand, crystal field splitting does
not occur and hence the substance is colorless
• For example, removal of water from[Ti(H2O)6]Cl3 on heating renders it
colorless. Similarly, anhydrous CuSO4 is white, but CuSO4 .5H2O is blue in color.
The influence of the ligand on the color of a complex may be illustrated by
considering the [Ni(H2O)6 ]2+ complex,
COLOR OF GEMSTONES
LIMITATIONS OF CRYSTAL FIELD THEORY
• The crystal field model is successful in explaining the formation, structures,
color and magnetic properties of coordination compounds to a large extent.
• However, from the assumptions that the ligands are point charges, it follows
that anionic ligands should exert the greatest splitting effect.
• The anionic ligands actually are found at the low end of the spectrochemical
series.
• it does not take into account the covalent character of bonding between the
ligand and the central atom. These are some of the weaknesses of CFT, which
are explained by ligand field theory (LFT) and molecular orbital theory which
are beyond the scope of the present study .