C H A P T E R

CO-ORDINATION
15 CHEMISTRY
LEARNING TECH.

Lanthanides Actinides
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lek;h Sm iM+h Pu
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xnxn Gd fleVk Cm
rc Tb fctyh Bk
fny Dy pedh Cf
gqvk Ho ,glku Es
vjs Er Qjkeks'k Fm
rqe Tm eapyh Md
;w¡ gh Yb fudyh No
yktokc gks Lu yM+dh Lr
d-Block
lqjs'kpanz frokjh VCR eas QSa dks ugha ihry
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
;kj tjk uacj feyk rk ------jk------jk------
La Hf Ta W Re Os Ir Pt Au Hg

yk gQ~rk oks jksbZ

fudkg Ni Cu Zn tekuk
i<+ks Pd Ag dher c<+rh gSA Cd dnznku
iafMr Pt Au Hg gksxk
298 INORGANIC CHEMISTRY
SALT:
(1) The compound, which contains acidic or basic radicals is known as salts.
(2) The compound, which is formed by the neutralisation reaction of acid and base is known as salt.
(3) The compound, which on hydrolysis gives acid and base is known as salt.

TYPEOFSALTS:
(1) Simple salt:
The salt, which contains one type of simple positive ion and one type of simple negative ion. For example, NaCl, KCl and
Na 2CO3.
(2) Mixed salt:
The salt, which contains more than one type of positive ions or more than one type of negative ions or both the ions are more
than one type. For example, microcosmic salt, NaNH4HPO4.4H2O.
(3) Double salt:
When two simple salt equimolar aqueous solutions are mixed together in equal amount and then are allowed to evaporate, then
residue which will left is known as double salt. When we ionize this salt, we will get three types of ions. In double salt one ion
should be common, either it should be positive ion or negative ion. For example, and (ALUM) K2SO4, Al2(SO4)3, 24H2O and
(MOHR SALT) (NH4)2SO4.FeSO4.6H2O.
(4) Complex salt:
The salt, which contains at least one complex ion or both the ions are complex in nature is known as complex salt.
For example, K4[Fe(CN)6], [Cr(H2O)6]Cl3 and [Pt(P4)6][PtCl4].

INTRODUCTIONTOCO-ORDINATIONCHEMISTRY

Ligand are electron pair donor as well as electron pair acceptor groups but carbonyl is the only the ligand which can donate as
well as accept electron pair. Except this ligand, generally other ligands are electron pair donor groups.

CLASSIFICATIONOFLIGANDS
(1) Charges resent on ligand: Ligands are of three types depending upon the charges present on them:
(a) Negative ligands
Ligands having negative charge on it and suffix 'O' will be added.
Cl– Br– F– OH– NH2– NH– N– – – H– C2O42–
Chloro Bromo Fluoro Hydroxo Amido Imido Nitrido Hydrido Oxalato
CO32– SO42– NO2 ONO– NO3– NCS– SCN–
Carbanato Sulphato Nitro Nitrito Nitrato Thiocynato-'N' Thicynato-'S'
(b) Neutral ligands
Ligand having no charge and it has no suffix/prefix.
NH3 H2O CO CS NO NS
Amine Aqua Carbonyl Thiocarbonyl Nitrosyl Thionitrosyl
(c) Positive ligands
Ligand having positive charge on it and 'ium' suffix will be added.
NO+ NO2+ NH2NH3+
Nitrosonium Nitronium Hydrozinium
CO-ORDINATION CHEMISTRY 299
(2) Number of co-ordinate bonds
Ligands are of six types depending upon the number of coordinate bonds:
(a) Monodentate ligand
Ligand, which can donate one pair of electrons to the metal ion.
For example, Cl–, NH3, H2O, SCN–, NCS– etc.
(b) Bidentate ligand
Ligand, which can donate two pairs of electrons to the metal ion.
The complex where chelate rings are present is known as chelate complex. More is the chelate ring more will be stability of
complex.

N
H2N–(CH2)2–NH2)
N

(Ethelene diamine)
(O-phenanthroline)
(c) Tridentate ligand
Ligand which can donate three pairs of electrons to metal ion.
H2N ( C H2) 2N H ( C H2) 2N H 2

M+
(Diethylene triamine)

(d) Tetradentate ligand

Ligand which can donate four pairs of electrons to metal ion.
H2 N(CH2) 2 NH (CH2) 2NH(CH2 )2NH2

M+

(Triethylnetetramine)
(e) Pentadentate ligand
Ligand which can donate five pairs of electrons to metal ion.
Ethylene diamine triacetato ion.

O O 3–
– O–C–CH C H2– C –O –
2
N–(CH2) 2–N
– O–C–CH H
2

O
(Ethylene diamine triacetato ion)

(f) Hexadentate ligand

Ligand, which can donate six pairs of electrons to metal ion.

O O 4–
– O–C–CH C H2– C –O –
2
N–(CH2) 2–N
– O–C–CH
2 CH–C–
2 O–
O O
(Ethylene diamine tetracetato ion)
300 INORGANIC CHEMISTRY
(3) Spectrochemical series
According to this, ligands are of two types:
(a) Strong field ligand
The ligand which will not follow Hund's rule and Aufbau principle is known as strong field ligand.
For example, CN–, CO, NCS–, NO2–, NH3, EtOH (ex). etc.,
(b) Weak field ligand
The ligand which follows Hund's rule and Aufbau principle is known as weak field ligand.
For example, Cl–, Br–, I–, F–, H2O, SCN– etc.

E.A.N. (EFFECTIVE ATOMIC NUMBER)

He 2
Ne 10
Ar 18
Kr 36
Kr 36
Xe 54
Rn 86
EAN = Atomic number of central metal – Oxidation state of central metal + 2 [Number of electron donated by ligands]
For K4[Fe(CN)6], EAN = 26 – 2 + 12 = 36.

WERNER'SCOORDINATIONTHEORY
Any complex salt has two types of valencies:
(1) Primary valency is the charge on coordination sphere.
(2) Secondary valency is number of coordinate bonds or coordination number.

NOMENCLATURE:
(1) First rule is applicable for those complexes where the simple type of positive ion and complex types of negative ion are present.

(a) First preference goes to the positive ion, which is present in outer sphere. [Write name not number]
(b) Second order goes to the ligands, if same type of ligands are there. So tri, tetra, penta and hexa terminology for 2, 3, 4, 5, 6
respectively.
(c) Third order goes to the name of the metal. (If positive ion is present in outer sphere or co-ordinate sphere has negative
charge, then you will write Greek name of metal atom and 'ate' suffix will be added.)
(d) Last order goes to the oxidation state of metal in Roman numericals within the small bracket.
(2) Second rule is applicable for those complexes where complex type of positive ion and simple type of negative ion is present.
(2) (1) (4) (3)
[Cr(H2O ) 6] C l 3 O. S.
Hexaaquachromium(III) chloride
(3) Third rule is applicable for those complexes where more than one type of ligands are present.
(a) If formula is given and we have to write the name, then charges does not matter there. We will write all these ligands
according to alphabetical order.
(b) If name is given and we have to write formula, then we will follow the following sequence for writing ligands after the metal
alphabetically.
Negative ligands
Neutral ligands
Positive ligands
NH4 [Co Br– Cl– I– NCS– (NH3) (H2O)]
(3) (4) (5) (6) (1) (2)

(4) Fourth rule is applicable to those complexs where the di, tri terminology creates controversy.
To avoid that controversy we will use bis, tris, tetrakis, pentakis instead of di, tri, tetra and penta.
M (NH2 – (CH)
2 2 – NH2 )2

Bisethelenediamine
CO-ORDINATION CHEMISTRY 301
(5) Fifth rule is applicable to those complexs where bridge ligands are present.
Beforewriting,thebridgeliganµdsterms is used.

Tetra aqua cobalt (III) µ-dihydroxotetraaquacobalt (III) sulphate

or
µ-dihydroxo octaaquadicobalt (III) sulphate
or
µ-dihydroxo bis (tetraaquacobalt(III)) sulphate

Tetraaquacobalt (III) µ-dihydroxotetraamminecobalt (III)sulphate

Tetraaquacobalt (III) µ-dihydroxoamminechromium (III) sulphate

Tetraaquacobalt (III) µ-amido-µ-hydroxotetramine chromium (III) sulphate

(6) Sixth rule is applicable for those complex where the complex type of positive ion and complex type of negative ions are present.

Tetraammine platinum (II) tetrachloroplatinate (II)

Tetraammine dichloroplatinum (IV) tetrachloro platinate (II)

ISOMERISM

Two or more than two complexes having similar molecular weight or molecular formula but their structural arrangements are different.
These forms are known as isomers and this phenomena is known as isomerism.
(1) Ionization isomerism (2) Linkage isomerism
(3) Hydration isomerism (4) Co-ordination isomerism
(5) Co-ordination position isomerism (6) Polymerization Isomerism
(7) Geometrical Isomerism (8) Optical isomerism

Ionisation isomerism
The isomerism which is due to change in position of ions is known as ionization isomerism.

[Cr(H2O)5Cl]SO4 BaSO 4
white ppt.

[Cr(H2O)5SO4]Cl AgCl
white ppt.
Linkage isomerism
[Cr[H2O]5NO2]SO4
[Cr[H2O]5ONO]SO4
[Cr[H2O]5NCS] SO4
[Cr[H2O]5 SCN]SO4
The isomerism, which is due to different linkages of atoms to metal is known as linkage isomerism
302 INORGANIC CHEMISTRY
Ambidentate ligand
The ligands where two or more than two atoms can donate electron pairs but at a time only one can donate pair of electron. Such
type of ligand is known as ambidentate ligand.
The complex where ambidentate ligands are always present shows linkage isomerism.
For example, NCS–, SCN– and NO2–, ONO–.

Hydration isomerism
Isomerism due to the change in position of water molecules in coordination sphere is known as hydration isomerism.
[Cr(H2O)6]Cl3 Pale green
[Cr(H2O)5Cl]Cl2.H2O Violet
Penta aqua chloro chromium (III) chloride hydrate
[Cr[H2O]4Cl2] Cl.2H2O Dark green

Coordination isomerism
Isomerism due to the change in coordination of ligands or metal is known as coordination isomerism.
[Pt(NH3)4Cl2] [PtBr4]
[Pt(NH3)4BrCl] [PtBr3Cl]
[Pt(NH3)4Br2][PtBr2Cl2]
Metal change
[Co(H2O)6] [Cr(CN)6]
[Cr(H2O)6][Co(CN)6]

Co-ordination position isomerism

CO
Cl2(HO)
2 2 Co Co(H2 O)2 Cl2 SO4
CO

CO
Cl(H2 O)3 Co Co Cl3H2O SO4
CO
The isomerism due to change in position of ligands in the co-ordination spheres is known as co-ordination isomerism.

Polymerization isomerism
[Pt(NH3)2Cl2] Monomer
[Pt(NH3)4][PtCl4] Dimer
[Pt(NH3)3Cl]2[PtCl4] Trimer

Geometrical isomerism
The isomerism, which is due to change in geometry of molecule is known as geometrical isomerism.
It is possible in square planar and octahedral complexs. It has two forms — cis and trans.
Types of geometrical isomerism in square planar complexes are:
(i) [Ma2b 2]
(ii) [Ma2bc]
(iii) [Mabcd]
(iv) [M(AB)2]
M = Transition metal
abcd = Monodentate ligand
AB = Bidentate ligand
CO-ORDINATION CHEMISTRY 303

Types of complex Coordination number Number of isomers

M(AA)2 4 1
M(AB)2 4 2
M(AA)cd 4 1
M(AB)cd 4 2
M(AA) a2 4 1
M(AB)a 2 4 1
M(AA)bc 4 1
M(AB)bc 4 2
Ma6 6 1
Ma5b 6 1
Ma2b 4 6 2
Ma2bc 6 2
Ma3b 3 6 2
Ma3b 2c 6 3
Ma3bcd 6 4
Ma2b 2c2 6 5
Ma2b 2cd 6 6
Ma2bcde 6 9
Mabcdef 6 15
M(AA)a 4 6 1
M(AA)a 3b 6 2
M(AA)a 2b 2 6 3
M(AA)abcd 6 6
M(AA)2ab 6 2
M(AA)2a2 6 2
M(AA)3 6 1
M(AB)3 6 2

Ma2b2

The above compound is cisplatin used in cancer therapy.

Ma2bc

M(AB)2

N N O N

Gly
M Gly Gly M Gly

O O N O
Cis Trans
304 INORGANIC CHEMISTRY
GEOMETRICAL ISOMERISM IN OCTAHEDRAL COMPLEXES
(i) Ma4b2

(ii) Ma3b3

(iii) Ma2b2c2

(iv) Mabcdef
= 15 geometrical isomers and 30 optical isomers.
CO-ORDINATION CHEMISTRY 305
(v) M(AA)2a2

(vi) M(AA)2ab

(vii) M(AA)a2b2

(viii) M(AB)3

OPTICAL ISOMERISM
(a) A coordination compound, which can rotate the plane of polarised light is said to be optically active.
(b) When the coordination compounds have same formula but differ in their ability to rotate directions of the plane of
polarised light are said to exhibit optical isomerism and such molecules are optical isomers. The optical isomers are pair
of molecules, which are non-superimpossible mirror images of each other.
(c) This is due to the absence of elements of symmetry in the complex.
(d) Optical isomerism is expected in tetrahedral complexes of the type Mabcd.
(e) These isomers are not ionisable due to their labile nature.
(f) Example: Bis-benzoylacetonato- beryllium (II)

H3C CH 3 H 3C CH3
C—O C—O C—O O—C
H—C Be C—H H—C Be C—H
C==O C==O C==O O==C
H5C6 C 6H5 H 5C 6 C 6 H5
306 INORGANIC CHEMISTRY
(g) Optical isomerism is not present in square planar complexes on account of the presence of axis of symmetry.
(h) Optical isomerism is very common in octahedral complexes.
(a) [Ma2B2C2]n± [Pt(py)2(NH3)2Cl2]2+

py py
2+ 2+
Cl Py py Cl

Pt Pt

Cl NH3 H3N Cl
NH3 NH3
Cis-d-isomer Mirror Cis--isomer
l
(b) [Mabcdef] [Pt(py)NH3NO 2ClBrI]

py py
py NO2 O2N py

Pt Pt

Cl NH3 H3N Cl
I I
d-isomer Mirror l-isomer
(c) [M(AA)3]n± [Co(en)3]3+

3+ 3+
en en
en

Co Co

en
en en
d-form Mirror l-form

en Co en en

'Meso' or optically inactive form

(d) [M(AA)2a2]n± [Co(en)2Cl2]+
3+
en en 3+
Cl Cl

Co Co

Cl Cl
en en
Cis-d-form Cis--form
l
Mirror

Trans form of [M(AA)2a2]n± does not show optical isomerism

CO-ORDINATION CHEMISTRY 307
(e) [M(AA)2a2]n± (Co(en)2NH 3 Cl]2+

en 2+ en 2+
Cl Cl

Co Co

H3N NH3
en en
Cis-d-form Cis--form
l
Mirror
(f) [M(AB)3] (Cr(gly)3]

gly gly

Cr gly Cr
gly

gly gly
Cis or trans-d-form Cis or trans--form
l
Mirror
SOME MORE EXAMPLE ARE:
[Cr(ox)3]3– ; [Fe(dipy)3]2+ ; [Cr(ox)2(H 2O) 2]¯ ; [Pt(en)3]4+
(a) A complex is formed in solution by the stepwise addition of ligands to a metal ion.
(b) This can be expressed as follows
[M] + [L] [ML]
(c) The stability constant K for this reaction is shown as
[ ML]
K=
[ M][ L]
(d) This metal can again get a ligand.
[ML] + [L] [ML2]
(e) The forthcoming stability constant is K1
[ ML 2 ]
K1 =
[ ML ][ L]
Its value is less than K.
(f) The higher the value of stability constant, stabler is the complex.
(g) The value of stability constant for some of the complexes are given below:
Complex Stability constant
[Cu(NH3)4]2+ 4.5 × 1011
[Ag(NH3)2] 2+ 1.6 × 107
[Co(NH3)6]2+ 1.12 × 1011
[Co(NH3)6] 2+ 5.0 × 1033
[AgCl2] – 1.11 × 105
[AgBr2]– 1.28 × 107
[Ag(CN)2] – 1.0 × 1022
[Cu(CN)4]2– 2.0 × 1027
[Fe(CN)6] 3– 7.69 × 1043
308 INORGANIC CHEMISTRY
STABILITYOFCOMPLEX
More is charge radius ratio, more will be stability of complex.
More is charge on central metal ion, more will be stability of complex.
Smaller the size of central metal ion, more will be stability of complex.
Mn 2+ Fe2+ Co 2+ Ni2+ Cu 2+ (Size decreases)
CN– and NH3 containing complexes are more stable than halogen containing complex because CN– and NH3 are strong Lewis base.
More is chelate rings, more will be stability of complex.
More basic is the ligand, more stability of complex.

CRYSTALFIELDTHEORY:
This theory determines the effect of different electrostatic fields caused by the different geometries of complex and different
basic strengths of ligands, on the energies of d-orbitals of the central metal ion.

Salient Feature of Crystal field theory

(1) The central metal cation is surrounded by ligands, which contain one or more lone pair of electrons.
(2) The ionic ligands (e.g., F–, Cl–, CN– etc.) are regarded as negative point charges (also called point charges) and the neutral
ligands (e. g., H2O, NH3 etc.) are regarded as point dipoles or simply dipoles, i.e., according to this theory, neutral ligands are
dipolar. If the ligand is neutral, the negative end of this ligand dipole is oriented towards the metal cation.
(3) The interaction between the metal cation and the ligands is regarded as purely electrostatic, i.e., the metal-ligand bond is
considered to be 100% ionic.
CFT as applied to Octahedral Complexes:
Splitting of d-orbitals in octahedral complexes

In case of free metal ion, all the five d-orbitals are degenerate, i.e., these have the same energy. Now let us consider an octahedral
complex, [ML6]n+ in which the central metal cation, Mn+ is placed at the centre of the octahedron and is surrounded by six ligands,
which reside at the six corners of the octahedron as shown in figure. The three axes viz., x-, y- and z-axes, which point along the corners
have also been shown. Now suppose both the ligands on each of the three axes are allowed to approach towards the metal cation, M n+
from both the ends of the axes. In this process, the electrons in d-orbitals of the metal cation are repelled by negative point charge or by
the negative end of the dipole of the ligands. (Remember CFT regards the ionic ligand as negative point charges and neutral ligands as
dipoles). This repulsion will raise the energy of all the five d-orbitals. If all the ligands approaching the central cation are at an equal
distance from each of the d-orbitals (i.e., the ligand field is spherically symmetrical), the energy of each of five d-orbitals will be raised
by the same amount i.e., all the d-orbitals will still remain degenerate, although they will now have higher energy than before. This is
only a hypothetical situation. Since the lobes of the two e g orbitals (i.e. dz2 and d x2–y2 orbitals) lie directly in the path of the approaching
ligands, the electrons in these orbitals experience greater force of repulsion than those in three t 2g orbitals (i.e., d xy, d yz and d zx orbitals)
whose lobes are directed in space between the path of the approaching ligands i.e., the energy of eg orbitals is increased while that of
t2g is decreased (Remember: Greater is the repulsion, greater the increase in energy). Thus, we find that under the influence of
approaching ligands, the five d-orbitals, which were originally degenerate in the free metallic cation are not split (or resolved) into two
levels viz. t 2g level, which is triply degenerate and is of lower energy, and eg level, which is doubly degenerate and is of higher energy
(See figure) . In other words, the degeneracy of the five d-orbitals is removed under the influence of the ligands. The separation of five
d-orbitals of the metal ion into two sets having different energies is called crystal field splitting or energy level splitting. This concept
of crystal field splitting makes the basis of CFT.
CO-ORDINATION CHEMISTRY 309
The energy gap between t 2g and eg sets is denoted by ∆0 or 10Dq where o in ∆0 indicates an octahedral arrangement of the ligands
around the central metal cation. This energy difference arises because of the difference in electrostatic field exerted by the ligands on
t2g and eg sets of orbitals of the central metal cation. ∆0 or 10Dq is called crystal field splitting energy. With the help of simple geometry,
it can be shown that the energy of t 2g orbitals in 0.4 ∆0 (= 4Dq) less than that of hypothetical degenerate d-orbitals (No splitting state
shown by dotted line in figure) and, hence, that of eg orbitals in 0.6 ∆0 (= 6Dq) above that of the hypothetical degenerated d-orbitals.
Thus, we find that t 2g set loses an energy equal to 0.4 ∆0 (= 4Dq) while eg set gains an energy equal to 0.6 ∆0 (= 6Dq). In figure, the loss
and gain in energies of t 2g and eg orbitals is shown by negative and positive signs respectively.

eg
z 2 x2– y 2

xy yz zx z2 x2–y 2 +0.6∆0=+6Dq
Energy increasing →

∆0 or 10Dq
-0.4∆ 0=-4Dq
xy yz zx z 2 x2– y 2
xy yz zx
t2g
t2g eg
Five degenerate d-orbital Hypothetical degenerate Splitting of d-orbitals
on the central metal d-orbitals at a under the influence
cation which are free higher energy level of six ligands in
from any ligand field octahedral complex

Crystal field splitting of d-orbitals in octahedral complex

Filling up of t2g and eg Orbitals with Electrons in Octahedral Complexes : High spin and Low spin Octahedral Complexes
For octahedral complexes containing weak ligands (i.e., weak field complexes), the energy difference, ∆0 between t2g and eg sets is
relatively small and hence the energy of all the five d-orbitals is supposed to be the same. Consequently, the filling of t 2g and eg orbitals
takes place according to Hund's rule, i.e., electrons pair up only when each of the five d-orbitals is at least singly filled. Thus, in case of
weak field complexes the distribution of d 1 to d 10 electrons in t 2g and eg orbitals takes place as d 1 = t 2g1eg0 (n = 1, S = n/2 = 1/2) ; d 2 =
t2g2eg0 (n = 2, S = 1) ; d 3 = t 2g3eg0 (n = 3, S = 3/2); d 4 = t 2g3eg1 (n = 4, S = 2) ; d 5 = t 2g3eg2 (n = 5, S = 5/2); d 6 = t 2g4eg2 (n = 4, S = 2) ; d 7 =
t2g5eg2 (n = 3, S = 3/2) ; d 8 = t 2g6eg2 (n = 2, S = 1) ; d 9 = t 2g6eg3 (n = 1, S = 1/2); d 10 = t 2g6eg4 (n = 0, S = 0). Here n = number of unpaired
electrons and S = resultant spin which is equal to n/2.
For octahedral complexes containing strong ligands (i.e., strong field complexes) all the three d-orbitals of low energy t 2g set are filled
up first and then the two d-orbitals of high energy eg set are filled. Thus, in this case, the distribution of d1 to 10 electrons in t 2g and eg
orbitals takes places as: d 1 = t 2g1eg0 (n = 1 S = 1/2) ; d 2 = t 2g2eg0 (n = 2, S = 1/2); d 3 = t 2g3eg0 (n = 3, S = 3/2); d 4 = t 2g4eg0 (n = 2, S = 1); d 5
= t 2g5eg0 (n = 1, S = 1/2) ; d 6 = t 2g6eg0 (n = 0 , S = 0) ; d 7 = t 2g6eg1 (n = 1, S = 1/2); d 8 = t 2g6eg2 (n = 2, S = 1) ; d 9 = t 2g6eg3 (n = 1, S = 1/2) ;
d 10 = t 2g6eg4 (n = 4, S = 0).
It may be seen that the weak field octahedral complexes of d 4, d 5, d 6 and d 7 ions have greater number of electron (S) than those of (same
ions) strong field complexes. It is for this reason that weak field complexes of d 4, d 5, d 6 and d 7 ions are also called high spin or spin free
complexes. Similarly, strong field complexes are also called low spin or spin paired complexes. Recall that VBT has called high spin
complexes as ionic (Pauling) or outer orbital (Huggin) complexes while the same theory has called low spin complexes as covalent or
inner orbital complexes.

Crystal Field Stabilization, Energies of Octahedral Complexes

We have seen that, according to CFT, under the influence of the six ligands approaching towards the central metal ion during the
formation of an octahedral complex, the d-orbitals of the central metal ion split into two sets of orbital viz. lower energy triplet (or trio)
t2g and higher energy doublet (or pair), eg. The t 2g set of orbitals is triply degenerate while eg set is doubly degenerate. The energy gap
between these two sets is equal to ∆0 (or 10Dq). The energy of t 2g set is lowered by 2/5 ∆0 (= 0.4 ∆0) or 4Dq while that of eg set is raised
by 3/5 ∆0 = (0.6 ∆0) or 6Dq relative to the energy of hypothetical degenerate d-orbitals. Thus, each electron occupying t2g orbitals
decreases the energy of d-orbitals by –0.4 ∆0 (= –4Dq) while that going into e g orbitals increases its energy by +0.6 ∆0 (= +6Dq). + signs
indicate respectively the decrease and increase in the energy of d-orbitals caused by their splitting under the influence of six. Now let
us consider a dx ion containing t 2gpegq configuration in which p is the number of electrons in t 2g set and q is the number of electrons in
eg set and x = p + q. Quite obviously:
310 INORGANIC CHEMISTRY
Change in energy (in terms of ∆0) for t 2gpegq configuration
= Loss in energy due to p electrons in t 2g set + Gain in energy due to q electrons in eg set
= –0.4 ∆0 × p + 0.6 ∆0 × q
= [–0.4 p + 0.5 q] ∆0 …(i)
Now since ∆0 = 10Dq, the above expression can also be written as
Change in energy (in terms of Dq) for t 2gpegq configuration
= [–0.4p + 0.6 q] × 10Dq
= [– 4p + 6q] Dq …(ii)

CFT as applied to Tetrahedral complexes: Splitting of d-orbitals in Tetrahedral Complexes

z
L
L y

Mn+ x

L
A tetrahedron is placed in a cube. The centre of the cube is at the centre of the tetrahedron at which is placed central metallic cation,
Mn+. Four corners of the cube are at the four corners of the tetrahedron at which are placed the four negative ligands, which have
been shown by circles with negative signs.
In order to understand the splitting of d-orbitals in tetrahedral complexes, a tetrahedron should be pictured as being placed in a cube as
represented in figure. It may be seen from the figure that the four negative ligands (represented by circles with negative signs) placed
at the four corners of the tetrahedron are located at the four corners of the cube. Thus, these four ligands are lying between the three
axes viz., x, y and z axes, which pass through the centre of the cube. Now the lobes of t 2 orbitals (d xy, d yz and d zx) are lying between the
axes, i.e., are lying directly in the path of the ligands. These orbitals will experience greater force of repulsion from the ligands than those
of e orbitals (d z2 and d x2–y2) whose lobes are lying along the axes, i.e. are lying in space between the ligands. Thus, the energy of t 2
orbitals will be increased while that of e orbitals will be decreased. Consequently, the d-orbitals are again split into two sets as shown
in figure. From which it may be seen that the order of energy of t 2 and e sets is the reverse of that seen for t 2g and eg sets in octahedral
complexes.
t2

xy yz zx
xy yz zx z2 x 2–y 2
Energy increasing →

+0.4∆0
No splitting state ∆t = 0.45
∆
z2 x 2–y2 -0.6∆0
xy yz zx z2 x2 –y2
(e)
t2 e
Five degenerate Hypothetical degenerate Splitting of d-orbitals
d-orbitals on the d-orbitals at a under the influence
central metal cation higher energy level of four ligands in a
tetrahedral complex

Crystal field splitting of d-orbitals in tetrahedral complex.

The energy difference between t 2 and e sets tetrahedral complex is represented as ∆t . It has been shown that ∆t < ∆0 , the cause of which
is that t 2 orbitals, although now closest to the ligands, do not point directly at the ligands, i.e., in an octahedral complex there is a ligand
along each axis and in a tetrahedral complex no ligand lies directly along any axis. For this reason and also because there are only four
ligands in the tetrahedral complex, while in an octahedral complex there are six ligands, the tetrahedral orbital splitting, ∆t is less than ∆0,
for the same metal and ligands and these are at same internuclear distances. It has also been shown that ∆t = 0.45 ∆0. Thus, the energy
level of the t 2 set is raised by 0.4 ∆t = 0.18 ∆0 while that of e set is lowered by 0.6 ∆t = 0.27 ∆0. The relational ∆t = 0.45 ∆0 also shows that,
other things being equal, the crystal field splitting in a tetrahedral complex will be about half the magnitude of that in octahedral complex.
Since ∆t is relatively small orbital splitting, spin-pairing in tetrahedral complexes in rather unlikely. Since ∆t< ∆0, crystal field splitting
favour the formation of octahedral complexes.
Note: The subscript g is not used for the splitting of d-orbitals in tetrahedral complexes because a tetrahedron has no centre of
symmetry. The symbol g is used for the ligands fields, which have centre of symmetry. (So instead of t2g and eg we can write t2 and e).
CO-ORDINATION CHEMISTRY 311
Splitting of d-orbitals in tetragonally distorted octahedral and square planar complexes
Before considering the splitting of d-orbitals of the central metal cation in these complexes, we should understand how tetragonally
distorted octahedral and square planar geometries are obtained from regular octahedral geometry. Consider a regular (symmetrical)
octahedral complex, [M(Lb)4 (La)2] in which La are two trans-ligands (i.e., La are the ligands lying along the z-axis) and Lb are the basal
ligands lying in xy plane. In this complex, all the bond axis distances (four M – Lb and two M – La distances) are equal [See figure]. Now
if two La ligands are moved slightly away from the central metal cation, then each of the four co-planar M–Lb distances, the symmetrical
shape of octahedral complex becomes tetragonally distorted octahedral shape [See figure]. Now if the two La ligands are completely-
removed away from z-axis, the tetragonally distorted octahedral shape become square planar [See figure (c)].

La La

La Lb Lb Lb Lb Lb

Both La ligands are moved Both La ligands are

M slightly away from M
M completley removed
M
Lb Lb Lb Lb Lb Lb

La La
Regular octahedral Tetragonally distorted Square planar
geometry octahedral geometry geometry
(M – L a = M – Lb) (M – L a = M – Lb )
(a) (b)
Now consider the splitting of d-orbitals in tetragonally distorted octahedral and square planar complexes. We start with the spliting of
d-orbitals in octahedral complexes. We have already seen that in octahedral complexes, the energy of dxy, dyz and dzx orbitals
(t 2g orbitals) is decreased while that of d and d orbitals (e g) orbitals is increased figure (a). Now in tetragonally distorted
x2 x2 − y2
octahedral complex, since the distance of the trans-ligands (La ligands) is increased from the central metal ion by removing them away
along the z-axis, d-orbitals along the z-axis (i.e., d orbital), in xz (i.e., d xz) and yz (i.e., d yz) planes experience less repulsion from the
z2

ligands as they do in the octahedral complex while the d-orbitals in xy plane (i.e., d xy and d orbitals) experience more repulsion
x2 − y2

than they do in the octahedral complex. Consequently, the energy of d xz, d yz and d zx orbitals decrease while that of d and d xy
x2 − y2
orbitals increase [See figure (b)]. Note that d yz and d xz orbitals will remain degenerate as they are in the octahedral complex. In square
planar geometry, the energies of d , d y and d zx orbitals again fall down while those of d and d xy orbitals rise up [see figure (c)]
z2 x2 − y2

(eg )
Energy increasing →

x 2–y2
z2 x–y
2 2
x 2–y2
∆2
xy
xy yz zx z2 x–y
2 2
+0.6∆ 0=+6Dq
z2
∆0 or 10Dq ∆sp
t2g eg z2
-0.4∆0=-4Dq
xy
xy yz zx ∆3
(t 2g ) yz zx
yz zx

Five degenerate Splitting of d-orbitals Splitting of d-orbitals Splitting of d-orbitals

d-orbitals on the in octahedral in tetragonally in square planar
central metal cation geometry distorted octahedral geometry
which are free geometry
from any ligand

Crystal field splitting of d-orbitals in octahedral, tetragonally

distorted octahedral and square planar complexes
312 INORGANIC CHEMISTRY
The crystal field splitting energy in square planar complex is denoted by ∆sp and is given by:
∆sp = E(d x2– y2) – E(d xz, dyz) = ∆x + ∆2 + ∆3 [See fig.]
The value of sp has been found larger than ∆0 (∆sp = 1.3∆0) because of the reason that d xz and d yz orbitals interact with only two ligands
in the square planar complexes, while in octahedral complexes the interaction takes place only with four ligands.
Applications of Crystal field Theory:
The following properties of transition metal complexes can well be explained on the basis of CFT.
1. Colour of transition metal complexes
It has been seen that the solution of transition metal complexes formed by metal cations having no unpaired electrons in d-orbitals (i.e.,
having completely filled or vacant d-orbitals) are colourless while the solution of transition metal complexes given by transition metal
cations having one or more unpaired electrons in d-orbitals are coloured. The colour of transition metal complexes having unpaired
electrons in d-orbitals can well be explained by considering the example of [Ti(H2O)6]3+ ion, which is an octahedral complex and has purple
colour. Now when white light is allowed to fall on this complex ion, the ion absorbs radiation from the white light (i.e., visible spectrum). The
maximum absorption takes place at a wavelength of 5000Å. The absorbed light of this wavelength is green and the transmitted light
corresponding to this absorbed light is purple, which is the colour of [Ti(H2O)6]3+ solution.
The cause of colour can also be explained on the basis of CFT as follows: We know that Ti3+ ion has the configuration t 2g1eg0. Now
when white light is allowed to fall on [Ti(H2O)5]3+ ion, the unpaired electrons present in t 2g set of orbitals move from lower energy t 2g
set to higher energy eg set, since the energy of the radiation absorbed by unpaired t 2g electron is the same as the energy difference
between t 2g and eg sets (see figure). This type of electronic transition from t 2g to eg level is called d–d or ligand-field transition, which
is the cause of the colour of [Ti(H2O)6]3+ ion.

eº g ↑ e'g
Light absorbed
∆a = E = 57 calories/mole
λ = 5000Å and
E = 57 calories/mole

t'2g ↑ tº2g
Ground state of Excited state of
[Ti(H 2O)6]3+ [Ti(H 2O)6]3+
(t2g1eg0) (t2g0eg1)
Absorption of light by [Ti(H2O )5]3+ ion involving a shift of an
electron from 2tg level to e g level. This transition [t2g1e g0 → t2g0e g1]
gives the [Ti(H2O)6]3+ ion its purple colour.
2. Magnetic moment value of complex compounds
CFT can be used to find out the number of unpaired electrons (n) in a given octahedral complex. The substitution of n value in
the spin only formula, µ = n (n + 2) gives the value of magnetic moment, µ of the given complex compound. From the
knowledge of n value of valence state of the central metal cation and the nature of bonding in the complex (i.e., whether the
complex is high spin or low spin) can be known.

EXAMPLES
1. [Ni(CN)4]2–
Ni +2 configuration
3d 4s 4p

Ni

Ni 2+

[Ni(CN)4]2–
CN¯ CN¯ CN¯ CN¯
d s p2 hybrid used
[Ni(CN)4]2– is square planar and diamagnetic. [NiCl4]2– , on the other hand, is paramagnetic and has tetrahedral geometry.
In this case, the VB treatment assumes that (i) the d-orbital occupancy remains the same as in the free Ni2+ ion and (ii) the
metal uses sp3 hybrids (involving 4s and 4p orbitals) for bonding with the ligands as shown below:
CO-ORDINATION CHEMISTRY 313
[NiCl4]2– is paramagnetic as there are two unpaired electrons.

3d 4s 4p

Ni

Ni 2+

[Ni(Cl)4]2–

Cl¯ Cl¯ Cl¯ Cl¯

s p 3 hybrid used
2. [Cr(H2O) 6] Cl3 Violet
[Cr(H2O) 5Cl]Cl2.H 2O Green
[Cr(H2O) 4Cl2]Cl.(H2O) 2 Dark green colour

3. CuSO4 + KF CuF2 + K2SO 4

↓ Green ppt.
CuSO4 + KCl CuCl2 + K2SO 4
Green solution

4. CuSO4 + KCN Cu(CN)2 Cu(CN)

2 2+ (CN)2
K3[Cu(CN) 4]
Because it produces K ions so with H2S it forms K2S but not Cu 2S due to lack of Cu 2+ ions.
+

5. (i) [Fe(CN)6]4–
Fe–26

Fe +2 → 3d 6

d2sp3
(Due to strong field ligand)

(ii) [FeF6]3–
Fe +3 → 3d 5

s p3d2
(iii) [Co(OX)3]3–
(iv) Co–27, 3d74s 2
Co +3 →3d 5

sp3d2
(v) [CoF6]3– , sp3d 2
Co +3 →3d 5

sp3d2
314 INORGANIC CHEMISTRY
6. Magnetic criteria of bond
K4[Fe(CN)6] Fe – 3d6

Fe +2 3d 6

d2sp3
This is diamagnetic in nature.

K3[Fe(CN)6]

d2sp3
Fe +3 → 3d 5
This is paramagnetic in nature.

ORGANOMETALLICS

The compound in which the organic group is directly attached with metal atom is known as organic nonmetallic compound and a
carbon-metal bond should be present there.
(1) Grignard reagent, RMgX
C2H5ONa not an organometallic compound.
(2) Zigler Natta salt
Mixture of TiCl4 + R3Al. It is a heterogenous catalyst and acts as catalyst for rubber polymerise atom reaction.
(3) Wilkonson's catalyst [{(Ph)3P}3Rh]Cl
It is homogenous catalyst and acts as catalyst for hydrogenation of alkanes.
(4) Ziese's salt

η2 potassium trichloro ethylene platinated (II)

(5) Ferrocene

η5 -biscyclopentadienyl iron (II)

(6) η 6 Bisbenzene chromium (0)

Ti+4

η1 biscyclopentadienyl η5 bicyclopentadienyl titanium (IV)

CO-ORDINATION CHEMISTRY 315
(7) Dimer of trimethyl aluminium

Hybridisation in Al is sp3.
(8) [Mn(CO)6]
[Ni(CO)4]

sp3 hybridization

Ni (28)
σ σ σ σ
π C π C C C
O O O O
Ni electronic configuration – [Ar] 4s 23d 8

O
C M M M M
C C C–
Ni
O O O+
C C
C
O O Bonding in metal and
O carbonyl
(Tetrahedral)
[Mn2(CO)10]

d2sp3hybridization

π π σ π σ σ σ σ
C C C C C
O O O O O

d2sp3hybridization

π π σ π σ σ σ σ
C C C C C
O O O O O
316 INORGANIC CHEMISTRY
Fe2(CO)9
d3sp3hybridization

π σ σ σ
C C C
O=C C=O C=O O O O

d3sp3hybridization

π σ σ σ
C C C
O O O