Chapter 6 Bonding CFT

CRYSTAL FIELD THEORY
The theory is introduced as a result of a failure VBT
in explaining some properties of complex. The theory is based on assumption that the formation of the bond between M-L is due to electrostatic attraction only, similar to the bond observed in an ionic crystal. The theory states that when a ligand with lone pair electrons (negative charge) approaching a metal ion (positive charge), all orbitals especially at the outermost shell in the metal are now being pressurised. The effect causes the energy level of the orbitals increase and the five degenerated d-orbital split to various energy levels depending to direction of ligand movement. 4/23/2012 Crystal Field Theory
Direction of M-L bonds z

z x x y y Tetraherdal octahedral x z
y
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Square planar
Effect on p- and s-orbitals

If we assume the incoming ligand approaching the
metal ion right on all axes. The pressure effects on s and p-orbitals in all direction are all uniform. L L L L L L L
L L L
L L

Thus both orbitals being pressurized (s- and p-orbitals)
are promoted to higher energy level. The shape and degeneration of the orbital are unchanged. 4p
4s E 4p 4s
Free metal ion
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Metal ion in complex

4
Crystal Field Theory
Effect on d-Orbital in Metal

d-orbital of metal also will be pressurized when
the ligands approach to metal via axis. Unlike s and p-orbitals, five d-orbitals in atom are not identical eventhough they are degenerate. Orientation of d-orbital can be divided to two groups The loops are on axis dx2-y2 & dz2 The loops are out of axis dxy, dyz & dxz.
Orientation of d-orbital
Orientation of d-orbitals
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CFT IN OKTAHEDRAL
COMPLEX
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ENERGY CHANGED OF d-ORBITAL IN OCTAHEDRAL COMPLEXES

eg
0.6 0.4
o or 10Dq atau 10Dq o t2g
Free -d Bebas Orbitald-orbital
d-orbital in a Orbital-d Ketika process of complex pembentukan formation Kompleks
d-orbital setelah Orbital-d after formation of a pembentukan complex Kompleks
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CRYSTAL FIELD SPLITTING ENERGY IN OKTAHEDRAL COMPLEX, o

Is a separation energy between eg and t2g
energy levels of split d-orbital caused by interaction with ligand.

The magnitude of the energy depends on
the present of ligand in the complex.

The larger of the energy shows that the
present ligand interacts strongly with dorbital of metal..

CRYSTAL FIELD SPLITTING ENERGY (CFSE) IN OKTAHEDRAL COMPLEX, o

For an octahedral complex, the magnitude of
~ 10,000 cm-1 (monopositive metal ion); 5,000 15,000 cm-1 (dipositive metal ion) 10,000 30,000 cm-1 (tripositive metal ion)
CFSE, o in most of the complexes are as follow;
The results show that the CFSE, o increases as
the oxidation number of a central metal ion increases.

DETERMINATION OF CRYSTAL FIELD SPLITTING ENERGY , 0 (10Dq)

Theoretical :
Using mathematical equation derived based on electrostatic interaction between the metal and ligand.
Experimental,
The value of 0 (10Dq) is determined from electronic spectrum of the complex. An band of maximum absorption normally observed in ultraviolet and visible regions. The band is identified by wavelength l or wavenumber formed as a result of a transition of electron from t2g to eg Orbitals. The transition of this type is known as d-d transition and usually observed in visible region..
ELECTRONIC SPECTRUM OF [Ti(H2O)6]3+

ultraviolet Visible Infrared
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Absorbance Wavelength of maximum absorption

300 400 500 Crystal Field Theory 600 700 12
Wavelength (nm)
DETERMINATION OF CRYSTAL FIELD SPLITTING ENERGY , 0

The energy
is calculated using Planck
equation;
E = 0 = hc / l
where h = Planck constant, c = light velocity and l is wavelength at maximum absorption of a complex
For majority of transition metal complexes,
the absorption occurred in the visible region reflecting formation of colour.

DETERMINATION OF CRYSTAL FIELD SPLITTING ENERGY , 0

As an example, the absorption of [Ti(H2O)6]3+
complex The solution of the complex gives violet colour due to a transition of electron from t2g to eg orbitals of Ti3+ ion. Ti(III) ion has an electronic configuration d1 in which [Ti(H2O)6]3+ complex, this single electron occupies in any three of t2g orbital
(t2g )1(eg )0
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(t2g )0(eg )1
14
THE CHANGES IN ELECTRONIC CONFIGURATION IN [Ti(H2O)6]3+

Configuration of [Ti(H2O)6]3+ complex
e g e g
t2g
Groundastate Ka a n ra eda s
t2g Ka a n ru e d state Exciteda te ja
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15
CACULATING CRYSTAL FIELD SPLITTING ENERGY, o OF [Ti(H2O)6]3+

The analysis of the complex by uv-vis spectroscopy
reported the wavelength of maximum absorption at l = 490 nm or 20300 cm-1 (violet solution) . Application of Planck equation
E = 0 (kJmol-1)
= (hc/l) (Avogadro number) = (6.6 10-34Js) (3 10-8 ms-1) (6.02 1023) 490 10-9 m
240 kJ mol-1
Thus, we conclude that two energy levels of t2g and eg are
separated by 240 kJ.
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16
LIGAND STRENGTH SERIES

CFT has used the o to determine the strength of a ligand
in which the higher is the stronger.
CFT estimates for a ligand with first raw transition metal
ion and having similar stereochemical, the o decreases in the order as follow, .
Ni2+ < Co2+ < Fe2+ < Co3+ < Fe3+ < Cr3+ < V3+ < Ti3+.
For a same metal ion, the ligand field strength decreases in
order
I-< Br- < Cl-< < SCN-< < N3-< < (CH2H5O)2PS2 < F- << (NH2)2CO < OH- << C2O42- < H2O < NCS- <, H- <<< NH2CH2CO2 < NH3 ~ C2H5N < en ~SO32- << NH2OH < NO2- << phen < CH3- << COCN< CO ~ CN-
The series later is known as spectrochemical series of

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ligand.
17
, cm-1 For Several Octahedral Complexes

Metal ion
Ti3+ V2+ Cr3+ Fe3+ Co3+ Fe2+ Co2+ Ni2+
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6F17,500(209) 16,100(193) 15,100(180) 14,000(168) 13,000(156)
6H2O
20,100(240) 18,500(221) 17,400(208)
6NH3
6CN22,100(264) 23,400(280) 26,600(318) 35,000(420) 34,800(416) 33,800(404)
21,600(258)
19,100(229) 22,900(274) 10,400(124) 9,300(111) 11,000(132) 8,500(102) 10,800(129)

18
CRYSTAL FIELD STABILIZATION ENERGY (ECFSE)

CFT found that the complex with low spin gives higher
stability than high spin complex. Therefore, the theory concludes that in all octahedral complexes, the complex is stabilized as electron occupies in t2g orbital while the complex is destabilized as electron occupies in eg orbital. The CFT estimates the magnitude of the stabilization energy (later known as crystal field stabilization energy ECFSE) of an octahedral complex is calculated using relation as follow,
ECFSE = [0.4p - 0.6q] o

Where p and q are number of electron occupying in t2g
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and eg orbitals respectively.
19

LIGAND FIELD STRENGTH
The CFT has recognized that in a complex the d-orbital of
metal is no longer degenerate but it splits to several energy levels because of interaction between the orbital with the surrounded ligand orbitals. Thus application of Hunds rule in a systematic filling of electron in an orbital is no longer valid but is determined by comparing the magnitude of splitting energy, o and electron pairing energy, Epair. Epair is an energy required for two electron to form pairing in an orbital.
If o > Epair , the electron tends to form pairing in d-orbital (low spin) If o < Epair , the electron tends to singly occupy in the d-orbital first before forming pairing (high spin) obey Hunds rule..

CFT found that those ligands in early
spectrochemical series exhibit high spin configuration with all metal ions. Thus < Epair. These ligands are classified as a weak ligand (weak field ligand)such as Cl-, F-, Br-, OH-, H2O
Similarly, ligands at end series give low spin
configuration complex with all metal ions. Therefore > Epair. The ligands are grouped as a strong ligand (strong field ligand) Such ligands include CN-, CO, NO2 etc.

The ligands located between these groups of
ligand (in the centre of spectrochemical series) are classified as an intermediate ligand (middle field ligand). The ligand may give low or high spin complex depending on metal ions present. Such example: NH3, ethylenediamine (en).
I-< Br- < Cl-< < SCN-< < N3-< < (CH2H5O)2PS2 < F<< (NH2)2CO < OH- << C2O42- < H2O < NCS- <, H<<< NH2CH2CO2 < NH3 ~ C2H5N < en ~SO32- << NH2OH < NO2- << phen < CH3- << COCN- < CO ~ CN4/23/2012 Crystal Field Theory 22
CRYSTAL FIELD THEORY MIDDLE FIELD LIGAND

The configuration of d-orbital with middle field ligand
depends on characteristic of central metal ion: Oxidation state size It is observed that the increase in oxidation state and size of metal, the complex formed tends to give low spin configuration and vice versa. Example complex of iron(II) and iron(III) with amonia [Fe(NH3)6]2+ high spin [Fe(NH3)6]3+ low spin

MAGNETIC PROPERTY OF COMPLEX
CFT has identified that the filling of electron in t2g and eg
orbitals of octahedral complex depends on o and Epair.
for o > Epair the complex tends to form low spin and high spin when o < Epair .
CFT also predicted that the complex with high spin tend to
enhance their magnetic property ( increase paramagnetic) while the low spin complex tend to diamagnet.
For complexes with configuration d1-d3, the filling electron
in the orbitals for all type of complexes are similar. In this cases, all complexes will show paramagnetic character.
o and Epair have no significant influence.
CONFIGURATION OF d-ORBITAL (d1-d3) IN OCTAHEDRAL COMPLEXES
eg
eg
eg
t2g d1
t2g d2
t2g d3
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25

For complex with configuration d4, d5, d6 and d7, the
magnetic property varies depending on ligand and oxidation state of metal. For these complexes, there are two possible electron arrangement:
High spin configuration where Epair > o observed in complex with low field ligand. The complexes enhancing towards paramagnetic. Low spin configuration where Epair < o observed in complex with low field ligand. The complexes enhancing towards diamagnetic.
eg t2g
High spin d6 paramagnet 4/23/2012
eg t2g
Low spin d6 diamagnet Crystal Field Theory 26

For complexes with configuration d8-d10, the filling
electron in the orbitals for all type of complexes are similar. o and Epair have no significant influence. In this case, d8 and9 in all complexes exhibit low paramagnetic while d10 is totally diamagnetic.
eg eg t2g d8
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eg t2g d9
t2g
d10
27
PROBLEM I CALCULATING ECFSE

Question
Determine ECFSE for two d6 complexes [Fe(CN)6]4- low spin [Fe(H2O)6]2+ high spin
Answer For [Fe(CN)6]4 Bagi [Fe(H2O)6]2+
- configuration t2g6 eg0 - configuration t2g4 eg2
o ECFSE ([Fe(H2O)6]2+) = 0.4 x 4 - 0.6 x 2 = 0.2 o

ECFSE ([Fe(CN)6]4- ) = 0.4 x 6 - 0 = 2.4
CFT EFFECT ON d-ORBITAL OF TETRAHEDRAL COMPLEXES

z
Incoming ligand approaching metal
through between axis.

CFT EFFECT ON d-ORBITAL OF TETRAHEDRAL COMPLEXES
0.4 0.6
Freed d-orbital Orbital-d bebas
Orbital-d ketika d-orbital during pembentukan complex kompleks formation
Orbital-d setelah d-orbital after pembentukan complex kompleks formation
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30
SPLITTING ENERGY, t IN TETRAHEDRAL COMPLEXES
t is a CF splitting energy of d-orbital in tetrahedral complexes. The magnitude of t is a different between the orbital energy level of t2g and eg and it is varied depending on ligand present. However, the splitting of t is small compared to . In all cases the ratio is t = 0.45 Therefore, all tetrahedral complexes exhibit high spin complex t < Epair.
Crystal Field Theory 31
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THE ECFSE EFFECT IN TETRAHEDRAL COMPLEXES

ECFSE = [0.4p - 0.6q]t Where p and q are the number of electron occupying t2g and eg orbitals respectively
OR

ECFSE = q (0.27 o) p (0.18 o) where o is splitting energy of a similar complex in octahedral field.
Crystal Field Theory 32
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PROBLEM 2, CALCULATING ECFSE

QUESTION
Calculate the ECFSE of [CoCl4]2- complex (Co(II) has d7 configuration)
ANSWER
ECFSE = [0.4p - 0.6q]t = [(0.4 x 4) - (0.6 x 3)] t = - 0.2t

ECFSE = q (0.27 o) p (0.18 o) = [(3 x 0.27) (4 x 0.18)] o = + 0.09 o
t2g eg
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33
THE ECFSE EFFECT IN SQUARE PLANAR COMPLEXES z

The energy level of d-orbital increase in the following order as a result of interaction with ligand in square planar field:
E dx2-y2 dxy dz2 dxz dan dxz
y Square planar
z
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34
THE ECFSE EFFECT IN SQUARE PLANAR COMPLEXES

d 2-y2 x sp
d xy d2 z d xz
Freed d-orbital Orbital-d bebas
Orbital-d ketika d-orbital during pembentukan complex kompleks formation
d yz
Orbital-d setelah d-orbital after pembentukan complex kompleks formation

35
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sp - SQUARE PLANAR
COMPLEXES
sp is a crystal field splitting energy of square planar complexes It is defined as a different between dx2-y2 with dxy energy levels. Those complexes (ML4) involved are derived from d8 metal ion with strong ligand. Such as CN-, CO, NO2, PH3. It is found that the square planar complex is more stable than tetrahedral.
CFT EFFECT COMPARISON

IN ALL COMPLEXES
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37
ADVANTAGEOUS OF CFT
The theory has successfully explains how electron configuration in d
orbital of all complexes are arranged. The theory has produced aspectrochemical series which explain the ligand strength. The theory has able to explain the colour formation in complex due to a transition of electron from t2g toeg. This type of transition is known as d-d transition. Able to estimate stablity of the complex based on magnitude of o where as o increase the stability of the complexes increases. The theory uses a calculated ECFSE to estimate relative stability among complexes.
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WEAKNESS OF CFT
The theory fails to explain why the F- ion
which is very high ionic property but displays less ligand field compared to water and amonia. The theory also fails to explain why the CN- and CO give very high ligand field effect with all metal.

Chapter 6 Bonding CFT

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Chapter 6 Bonding CFT

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CRYSTAL FIELD THEORY

The theory is introduced as a result of a failure VBT

Direction of M-L bonds z

Effect on p- and s-orbitals

CRYSTAL FIELD THEORY

Metal ion in complex

Crystal Field Theory

Effect on d-Orbital in Metal

Crystal Field Theory

Crystal Field Theory

ENERGY CHANGED OF d-ORBITAL IN OCTAHEDRAL COMPLEXES

o or 10Dq atau 10Dq o t2g

Free -d Bebas Orbitald-orbital

d-orbital in a Orbital-d Ketika process of complex pembentukan formation Kompleks

d-orbital setelah Orbital-d after formation of a pembentukan complex Kompleks

Crystal Field Theory

CRYSTAL FIELD SPLITTING ENERGY IN OKTAHEDRAL COMPLEX, o

energy levels of split d-orbital caused by interaction with ligand.

the present of ligand in the complex.

present ligand interacts strongly with dorbital of metal..

CRYSTAL FIELD SPLITTING ENERGY (CFSE) IN OKTAHEDRAL COMPLEX, o

CFSE, o in most of the complexes are as follow;

The results show that the CFSE, o increases as

the oxidation number of a central metal ion increases.

DETERMINATION OF CRYSTAL FIELD SPLITTING ENERGY , 0 (10Dq)

ELECTRONIC SPECTRUM OF [Ti(H2O)6]3+

Absorbance Wavelength of maximum absorption

DETERMINATION OF CRYSTAL FIELD SPLITTING ENERGY , 0

is calculated using Planck

For majority of transition metal complexes,

the absorption occurred in the visible region reflecting formation of colour.

DETERMINATION OF CRYSTAL FIELD SPLITTING ENERGY , 0

Crystal Field Theory

THE CHANGES IN ELECTRONIC CONFIGURATION IN [Ti(H2O)6]3+

t2g Ka a n ru e d state Exciteda te ja

Crystal Field Theory

CACULATING CRYSTAL FIELD SPLITTING ENERGY, o OF [Ti(H2O)6]3+

Thus, we conclude that two energy levels of t2g and eg are

separated by 240 kJ.

Crystal Field Theory

LIGAND STRENGTH SERIES

in which the higher is the stronger.

CFT estimates for a ligand with first raw transition metal

For a same metal ion, the ligand field strength decreases in

The series later is known as spectrochemical series of

Crystal Field Theory

, cm-1 For Several Octahedral Complexes

6F17,500(209) 16,100(193) 15,100(180) 14,000(168) 13,000(156)

6CN22,100(264) 23,400(280) 26,600(318) 35,000(420) 34,800(416) 33,800(404)

19,100(229) 22,900(274) 10,400(124) 9,300(111) 11,000(132) 8,500(102) 10,800(129)

CRYSTAL FIELD STABILIZATION ENERGY (ECFSE)

ECFSE = [0.4p - 0.6q] o

and eg orbitals respectively.

Crystal Field Theory

CRYSTAL FIELD THEORY

CRYSTAL FIELD THEORY

CRYSTAL FIELD THEORY

CRYSTAL FIELD THEORY MIDDLE FIELD LIGAND

CRYSTAL FIELD THEORY

orbitals of octahedral complex depends on o and Epair.

CONFIGURATION OF d-ORBITAL (d1-d3) IN OCTAHEDRAL COMPLEXES

Crystal Field Theory

CRYSTAL FIELD THEORY