rn

Introduction
• Tran a1'tion metals have property to un d ergo '~om iJ Iex ,.,o rm at,·on · It 's beca use th ey form a large nurnh_
•itr of
coordination compounds.-
·th study of coordination compounds 0
• Coordination chemistry: Branch of chemistry whi ch dea Is wi r coll'lpJ.
e%
compounds . .
• • I . rround ed by number of oppositely char
Coordination compounds: conta in a ce ntral metal ion a tom su ged ion fJr
neutral molecule .
e.g. [Cu(NH 3 ) 4 ]2'
Central Metal ion __J L Neutral molecule
Chlorophyll (coordination compound of Mg
Coordination Red pigment Haemoglobin = (Fe)
compounds Catalyst
~ Analytical reagents

Werner's Theory of Coordination Compounds I

Alfred Werner, a Swiss chemist, framed his idea about the structure of coordination compounds .
~ (1) Mellace elements exhibit two types of valence.
Basic postulates
of ~ (2 ) Primary and secondary valence.
~ (3) Every metal tends to satisfy it's primary and secondary valence.
Werner's
~(4) Every metal has a fixed number of secondary valence.
Theory
_______ _ __ _, ~ (5) Secondary valence is always directed towa rds fixed position in space .
• Salient features:
Prima Valence Seconda Valence
(J) It is know as ionisable valence. (1) lt is called a s auxiliary / subsidiary / residual / non-
ionisabl e valence. lt is also termed as coordination

---- dotted line.

Outer s here 2 nd s here is ionization s h ere. Inner s here l s, s here is the coordination s here. ,
G.r-oups present in this sphere are loosely Groups present in thi s sphere are firmly attached ;
bound and the can easil se arated as ion . cann ot be easil se arated . , 1

(5) Example of salt= PtCI , CoCl 3 , CuCl 2 and AgCI. (5) Exampl e = [Co(NH 3)i', [Cu(NH 3 ) 4 f and [Ag(NH 3)iJ'.
1

Primary valen ce of Pt , Co, Cu and Ag is +4 , 3, 3 2

Secondary val en ce of Co ' , Cu ' , Ag· is 6, 4, 2 !
2 , 1 respectively .
res ective l . It corres onds to coordination number.
Werner's Theory in the Light of Modern Electronic Theory of Valence
* According to Wern er in a complex th ere are two sph ere of attracti on . Inner s phere is coordination sphere where 1

groups are firmly a tta ch ed to metal ion and outer sphere is ioni sati on sphere wh ere groups are loosely bonded ;
and can be separated by di ssolving a compl ex in suitabl e solvent.
* Werner introduced a s quare bra cket [ ] fo r coordin a ti on s phere of compl ex compound. . 1

e .g. In complex [Co(MH 3 ) 6 ]C1 3 . Six NH 3 molecules are in coo rdin ati on s phe re while three chloride ions are in
ionization sphere.
• Application of Werner's theory to Co(l11) amines:
For CoCl3 · 6NH3 / /Co(NH3 )J Cl3 : .

( l) On reaction with AgN0 3 gives precipitate whi ch co rrespond s to three er . These 3Cr must be in ionization
sphere and repre sent primary valen ces of Co . . . . he I
(2 ) On reaction with HCI , ammonia is n ot removed hen ce all sue NH 3 are in coordination sphere sat~
secondary valence of Co .

(396)

)
 . ·di·,1c1iio11 (u 111po1111d1
(/IOI 397

(3) It c-ont a in four partic-k; ~~ i~g t .- .

. . , o c1yoscop1c- s t url y
4) In 111trobe n zen e it s m olcc ul ·, - c-
( n1
,.1 • • • •
Ol111ll C' t1v1t'\1 · d
!Co(NH 3 ) 6 JC1 :i a nd it io ni zes ns J co rn:s pon s to s ix c ha rges . I fen ce it mu st be in th e form

!Co (NH 3 )c,Cl_, ~ ICo (NH _, )cJ ·' + JCI

Similarly for CoC l_,- 5 NH 1 , CoC L-4NH
,, a nd CoCl NH
,l
__
3
, _ _ ;1 , the fea tures of coba lt a min es is as follows:
., ·_
- composition No. of er precipitated -
No. of ions Total charge - Molar conductance
by AgN0 3 particles
C oCl3 · 6NH .,
_23____
--- - 4
- -- --- - .
Ohm- 1 mor 1
---
C oC13 · 5NH 3 -
J
-- - - --6 - - . 390 [Co (NH 3 j,,J3', 3Cr
- ------- 4 26 1 [Co(NH 3 ) 5 Clj2 ' , 2cr
- CoC13 · 4N H3 l 2- - - - - - -
2 l 02 [Co( NHJ 4 Cl2 j3' , Cr
CoC13 · 3 NH 3 0
0
- 0
0 [Co(NHJh c1_ ii3·,
la
11!1111111 Ligand s
Ligands = liga n e ~ b ind
, The molecul es or ions whic h forms coordinate b d ·h
on s wit m etal atom · · .
called ligands. or ion m a coordination compound s a re
2
e.g. In ICu(NH 3 ) 4 ]' a nd IFe(CN) 6 r 2
, NH :i and CW are ligan ds .
, Classification of ligands:

On the basis On the basis of number

of chancre of donor sites
Negative ligands Monodenate: On ly on e

t
<:belting ~igands: A bidentate or polydentate
cr , Br" , NH; donor site
2
hgand which forms more than one coordinate
H20 , 0 -
bond in su ch a way that a ring is formed .
1
Bidentate: To donor sites CH? - NH 2
Positive ligands I -
(COO-b, CH2 - NH 2
NO; , NH; , NO ' CH 2 - NH 2
I
CH 2 - NH 2 (Ethylenediamine)
Neutral ligands (E1 hylen ediarnine) Ambidentate ligands: Monodentate ligand which
H2~ , NH 3, CO Polydentate: More than contains more than one coordinating atom.
two donor sites M t-- 0 - - N = 0
EDTA (Hexadenate) ,1/ 0
M t- N:1/'
"-o-
'JW Coordination Number: Ligancy (CN)
Ill Coordination Number: Th e number of ligands which are directly attach ed to metal atom ion in a coordination
compound/ compl ex .
e.g. In K3 1Fe(CN) 6 ], six CN (ligan d s ) with Fe :. CN of Fe 3 ' is 6.
121 Metal chelates: In m e tal ch elates , CN is number of electron pairs involved in bonding between liga nds and
metal atom/ion .
e.g. In ICu(en)l ' the 4 electron pai rs are bonded between Cu 2 ' and ethylene diamine (en). Hence CN of Cu 2 ' is 4 .
I 131 Complex ion: Complex ion is charged radical form ed when metal ion directly linked to ligands (neutral or - vely charged)
e.g. 1Cu(NH 3)S'
4 Coordination entity: Ce nt ral m e tal ion/ a tom with ne ut ra l molec ules or ion .
1)
e.g, IFe(CN) l - and [Co(NH 3 ) 6 ]' 3
(S) Coordination sphere: Cen tra l metal ato m or ion and li gand s directly a ttac hed to it are w1;tten inside square
bracket is coordination sph e re.
e.g. In K3 !Fe(CN) 6 ], coordin a tion s ph ere is ife(CN) f,J
161 Oxidation number of central metal atoms: Oxidation numbe r is an electric c harge on metal a tom/ion which
has or appears to have when it is bond ed with liga nd.
e.g. In !Cu(NH 3) 4 ]2+, th e oxidation number of Cu is 2 a nd written as Cu(II)
r~------------~~--------
(7)

~
Coo rdin a tion compound (co mpl exe s )

-- - -
I - - - - ..1 ,
'V

He tero le pti c c omplexes

Ho moleptic comp lexes
(contain more than one kind of ligands)
(contain s sa m e kind of ligancf'i 2
e.g. [C o(NH -1) 5 C lj'
e.g . /Co(NH , )fJ .1
(8) Coo rdin a tion co mpound are of three type s:

~--- --- --t------- Anioni c Compl e xe s

V
Neut r al Complexe s
Cationic Compl exes e.g. [Pt(NH-ibCl 2 ]
e.g. K/4[Fe (C N) ,,]
e.g. [Ni(NH 3 ) 6 )Cl2
(Complex ion carries no rtet

1l 1l chnrge)
[Ni(NH3)6]2· + 2cr [Fe(C N) 6)--4 + 4K '
·
(Complex zon ·
carnes ··
ne t pos1twe (Comp Lex i·on carries net negative
~~ ~~ . .
(9) Charge number of complex ion: is the algebraic sum of charges earned by central metal atom/Ion and liganch
e.g. [Ag(CNbr 1 Charge of Ag+ 2 x charge on cw
(+]) + 2 X (- 1)
+1 - 2
-1
(10) Coordination polyhedron: It is arrangement of ligands about central metal atom/ion in the space .
(i) Square planar (ii) Tetrahedral (iii) Triagonal bipyramidal (iv) Octahedral (v) Square pyramidal
Cl Cl L L L L
""/ I 1/ L L~ / /L L"' //L
Pt M L-M M M
c1 / ""-c1 ~ I "' L I~ L L/ I~ L L/ "'L
L L L
11 Difference between double salts and coordination com ounds:
Coordination com ound Double salt
A coordination compound may or may not be ionic but A double salt is ionic compound and does not contain
the com lex art alwa s contains coordinate bonds. an coordinate bond.
A coordination compound (complex) retains its identity A double salt loses its identity in the solution.

Characteristic of Complex Ion

(l) Chelate complexes are more
stable than non -ch ela ting f=.-____ (3) Central metal atom is generally
transition metal,
complexe s. ---------------
Characteristics of (4) Metal ion loses its individual
1-----:.
complex ion properties and has
(2) Net charge = algebraic s um of
charges carried by ce ntral properties of complex ion .
metal and ligand s bonded to it (5) In the solution complex ion has
identity _
Sidgwick's Electronic Theory
As per Sedgwick 's con cept eac h ligand donate e lec tron pairs to the central m etal ion and thus form number
coordinate bonds .

e.g. C u 2+ + 4 NH 3 Cuprammonium ion,

 . ation Compounds
cool'd111
399 \l
~ective Atomic Number (EAN)

Number o_f electron with ce ntral· metal atom/ion

alter gammg e- from ligands.

EAN = z - X + Y Z = At. No. of metal

X = No. of e lost in the formation of metal
Y = No . of e- donated by ligands
e .g. ICo(NH 3)6]3' (Co= 27)
EAN
EAN = (27 - 3) + 6 x 2 = 36

In a c~mplex, the central metal atom/ion accepts the e-

from h_gan?s fill the total no. of electrons around central
metal !On is equal to at. no . of next inert noble gas atom.
e.g. IFe(CN) 6r4. [Co(NH 3)6]' 3 EAN = 36
Some complexes ion
Fe(CN) 6- 3 , [Cu(NH 3)4 ]' 2
EAN = 35 * At. no. of next rare gas (Kr)
IUPAC Nomenclature of Mono nuclear Coordination Compounds
• Rules applied for naming coordination compounds as per IUPAC are -
t
G)
Naming of Positive ion (cation) named 1st followed
com ounds by negative ion (anion)

Naming complex (a) Cation = name of ligand is followed by metal ion and oxidation state of
metal is written in bracket.
ions
(b) Anion = name of ligand is followed by name of metal ending with suffix -ate.
(c) Neutral (non-ionic) = write as one word.

Alphabetical order If more than one ligands present, then name it alphabetically .

For anionic Names of ligands end with -0- and for the complexes containing cationic or
ligands neutral ligands are written in the same way except for H 20 (aquo) NH 3 (amine),
CO (Carbonyl), NO (nitrosyl) .

[ Prefixes Wh e n two or more same ligands are present then prefix will be di, tri, tetra and
for ch elate ligands = bis , tris, tetrakis

[ Preference of ligands J s t n ega tive ligand then ne utral and lastly positive ligands.

Isomerism in Coordination Compounds

Isomerism
Isomers are compounds that have the same chemical formula
but a different arrangement of atoms in the space

(a) Structural isomerism (b) Stereoisomerism

Isomers have different arrangement of ligands Different atoms or groups occupy different
around the central metal atom spatial positions around the central metal atom.
 U1tam 's MHT-CET (Ch .
eni1.111y,
400
---
(at
--I
Structural isornerisrn
- - ---

Ionisation
-=-_ l_ _ - -
Hydra te I
L~,ka~e-J
isorn e ris f!!_
Coordinate
isomerism
isomcri~ _ Wh e n. a.n. a.mbidenta.te When both positive
isomersm . . Q7td
1 · h d,ijjrrer in th e h d to negatwe zon.s of a salt are
Compounds , which give Isom ers, w ,11c J' ligands is a.tta.c _e
number of wa te r molecules t 1 through different complex ions and t
different ions in solution I.Vo
isomers differ in the
due to the exchange of ions at-ta ched to the me tal atom me .a
a.toms
th
a.n
the
or ion as ligands . compounds a.re s aid to be distribution of ligands in
in coordination sphere and
two complex ions.
counter ions are called jCr(H 2O)<,]C l:i, linkage isomers.
[Co(NH 3),;][Cr(CN) 6 ],
ionization isomers. jCr(HP) ~Cl]Cl2·HP [Co(N0 2)(NH3)5]CI
[Co(CN) 6 ][Cr(NH 3 ) 6 ]
[CoBr(N H3 ) 5 ]SO 4 , [Co(ONO)(NH3)sCI
[CoSO 4 (N H3 ) 5 ]Br
(b) Stereoisomerisrn

Op tical isomerism
1 Geometrical or cis-trans ] . This isomerism arises due to
· 'ti
posz ans ⇒
ClS
If two identical ligands occupy ad1a.cent · non-superimposable m irror images
If occupy opposite positions ⇒ trans
I t J
-Ji, Only in octahedral complexes with
In square planar In octahedral 2 or 3 bidentate ligands
shown by
shown by
I
I
~
MABX2 f cis trans
M~XY MA~X2 I

I I optically inactive
MABXY
f t f t
l-form
1

trans d-form
Cis
f t
If all three similar groups occupy If three similar groups are present around meridian
Adjacent position then Jae-isomer of octahedral then mer-isomer
• Geometrical isomerism is not shown by tetrahedral complexes.

1111 Bonding in Coordination Compounds /

The formation of coordination compounds and their various properties can be explained by
faJ Valence bond theory (VBT)
fbJ Crystal field theory (CFT)
fcJ Ligand field theory (LFT)
fd) Molecular orbital theory (MOT)

Valence Bond Theory (VBT) I

-
( 1) Central metal ion provide s definite no. of vacant orbitals, s, p and d for the formation of coordinate bond with
ligands.
(2) Coordination Number = vacant orbital provided by central metal atom .
Hybri sization
(3) Vacant orbitals --=----------4 same number of hybrid orbitals.
(4) Each ligand = one orbital containing a lone pair of e-.
(5) Coordination bond between metal a nd ligand = vacant orbital of metal · . . al f the
ton over1aps with filled orbit s o
ligands
(6) Geometrical shapes
Hybridisation Geometrical shape Examole
sp3 Tetrahedral
sp 2d/dsp 2 Square planar
Octahedral
Coordina!ion Compn1111d., 401

--------- - - ----------~-- ------

r(7) Strong coo rd ina te bond = Greater ov; rl appln~- ~~~e n orbita ls .
I (8) Inner complex= If (n - JJd orbitals used for hybridization.
outer complex = If nd orbita ls u sed for hybrid iza tion .
(g) Pararnagnr.tic = If centra l meta l 'at om o1- complex
.
have oneor more unpa ired e·
I Diamagn eti c = lf centra l metal a tom of complex have pa ired e .
I (JO) Spin pairing = When st rong lleld ligands like NH:1 and CN- are involved in the formation of complexes. th ey
causes pairing oft:'- present in metal ion. 111is procrss is ca lled sp in pairing.
- Structures of Complex Compounds b;sed 00 VBT -,
- (1) Formation of [Ni(C0)4) Nickel tetra carbonyl: (2) Formation of (NiCJJ 2 :
The electrons present in 4s orbital of Ni are shifted 3d 4s 4p
to 3d o_rbital in presence of CO (ligand) . The 4s and Ni (ground / 1l /1l /1l / t /I / DI] / / / /
4p orbitals (vacant) undergoes sp 3 hybridisation to t t )
s a e
form 4sp 3 hybrid orbitals.
3d 4s 4p
~
Ni (ground /
3d
1l /1l /1l /I II / [ill LLLJ
4s 2
Ni• (ground
state)
I1l I1l /1l /t /t / D /,____/,____/,____/
state)
t ___ .__ --. 3d , 4s 4p ;
3d ,4s ~ '
Ni'2 ~ncnsro I1l I1l /1l /I /t I/D / / / //
Ni (Hybridised
/1l /1l /1l /1l /1l l ! □ LLLJi ~~~ I
I
I ______ _ ____ __ ____
I
I
!
state) I
I
I
I
-----------------1 sp 3 hybridised orbitals
3
sp hybridised orbitals 2
sp 3 hybrids orbitals of Ni overlap with filled orbitals (NiCll / 1l /1l /1l I 1 11 I /x/x/x/x/
of CO (ligand) to form coordina te bonds. sp 3 hybridisation
i Ni(COJ4 1t l1l lt lt l1l l r--1
x.---1x-r-1x~l~xI X ~ Electron pair from er
10 electrons of Ni (paired) sp 3 Hy b n!d 1sa
. ti Geometry: Tetrahedral
on
Magnetic property: Paramagnetic
X ~ Electron pair from CO. (Two unpaired electrons)
Geometry: Tetrahedral
Mai!netic property: Diamagn etic
(3) Formation of [Ni(CN)J-2 : (4) Formation of (Cu(NHJ4)' 2 :
3d 4s 4p 3d 4s 4p
Ni (grou nd I1l I1l I 1l / I I I I ill] '--I__.__I___._I__,/ Cu (grou nd / 1l I1l I 1l I 1~ I i I ill] I I I I
state) state)
3d 4s 4p 3d 4s 4p
Nr 2
lground I1l I1l /1l I1' I1' I D I / / J
2
Cu • lground
state)
I1l I1l /1l /1l Ii / D . / I \ \
state)
3d : 4s ~ 3d 1 4s 4p:
Ni (Hybridised
l1l /1l /1l /1l j I
I O LLU I
Cu,, Hyb~sro I1l /1l \1l I1l I I D I \ \I \
state) I
L- - --------------- ~
dsp 2 hybridised orbitals
I

slate) r--~--.----.-. LP~-;;;t;,a;;;d ~;b;, ~)

INi(CNV2 lr--
t -r-11l--.--11--r
l l--,
1l I I X I X I X I X I· □ ICu(NH~ /' I1l I1l I1l I1l I I X / X \ X \ X I [I]
2
dsp hybridi sa tion dsp 2 hybridlsa tJon
x -➔ Electron pair from NH:i
x ----, Electro pair from CW
Geometry: Square planar Geometry: Square planar
Magnetic property: Diamagnetic Magnetic property: Para magnetic
(No unpaired electron s) (one unpaired electron)
 402 U1tam '.1· MHT-('£T 1 .
Chr:n,
11,~.

(6 ) Formation of [CoF6 r 3
:

l1lj1lr31rr/rj Im [TI]
1d 4s 4p
Co (~round
s tu tt·)
l l
111,j ll i i f l I I11I I 1 I Co
(grou nd state) r-- -------------- - - -

Co ' ~,und
sta te)
111 ] rr'~I rIrI 1
.
] I j <rj
___ __ ____________ ___- - - - - -,
I Co" [ lD'I~Ff1J
1
{Hybrid ised sta te)
PJt!J_~ ~-
., 2
s p 'd hybridi sed orbitals
-~ .

Co •o;, bridmi
st a t e)
I 1lilll J~tI J [] [ ''.1n
:
1
'-------------------------~:
i CoFJ , ffil r I;ifru ~ y : xx
s p 1 d 2 hy bridisation
,,q
cc
4d

2 3
d s p h ybridised orbitals x Electron pair from
----1 r
1co(NH.,l( /1l l1l l1l l /x/xl xlxlx/xj Geometry: Octahedral
Magnetic property: Paramagnetic
d 2 sp 3 hybridisation
x ~ Electron pair from NH 3 {Unpaired electrons)
Geometry: Octahedral

1
~;;.M:~~;~~~~~~~~~~
: ;D~im~a~ ;;e~tic;;N~o~un~;~arr~·~ed~~el~e;ctr;o~n~s;~::~:i.~~:;::~~~~~~i~~l - - - - - - - - - -
•§@ Magnetic Properties of Coordination Compounds based on VBT
1
• !fe(CN) 6 r 3 is paramagnetic (1 unpaired electron)
• !fe F6r 3 is paramagnetic (5 unpai red electrons)
I • !CoF6r 3 is paramagnetic (4 unpaired electrons)
1• !Co(C 2 0 4 b]"'1 is diamagnetic
!Co(C 2 0 4 r undergoes d 2 sp 3 hybridisation (I nner orbital complexes).
3 3
!Fe(CN) 6r ,
3 3
!feF6 r , (CoF6r undergoes sp 3 d 2 hybridisation {outer orbital complexes)
Limitation of VBT:
Cannot explain order of reactivity of
Cannot explain spectra] property
mner orbitals of d 3 , d4, d 5 , d 6 ions. (colour)
® G)
Cannot predict exactly tetrahedral / Does not explain magnetic moment
squa re planar structure of 4-coordinate. due to orbital motion of electrons.

Does n ot di s tinguish weak and Cannot explain formation of inner

s trong fi eld ligand . and outer complexes for same metal
ion wi th same oxidation state.
Ca nn ot explai n thermodynamic and <E@
kin eti c s ta bili ty of coordination complexes. ~ Cannot always explai ns geometry

•fW Crystal Field Theory (CFT) I

CFT = proposed by Beth e a nd appli ed by Schl app and Penny.
According to thi s th eory,

~ Higher energy level

Wh en liga nd a pproach towa rd ce ntra l metal atom/ion 5 degenerated orbits ~
Split in to 2 leve l >~
~ Lower energy level
Th ese separated group s a re call ed t 2g {dxy, dyz a nd dxz) a nd eg (dx2 _ y2 and dz2).
Crystal field splitting: is splitting of 5 dege nera te 'd ' orbitals of metal ion into 2 sets of orbital having different
en ergies .
* Difference in th e energy levels be twee n th ese 'd' orbitals is taken to be~ or lODq.
Splittin g of orbitals depends upon geometry of complex .
L___ _ _ _ _ _ _ _ _ _ _ _ __ __ _ _ _ _ _ _ _ _ _ _ _____
___,
 . ;
11 0 11
( ·0 111;101111ds 403
( ·ool'l I" "

O f s ; ! ! ~_t _Fea!ure·~- ~i C~ ·1 . .
(i) The ce ntra l _m e t a l a t o m / to n m a c ompl e x 1s s urround e d by a tom s or g roup of a to m s ca ll e d liga nd s whi c h are
eithe r n ega tive ly c h a rge d (C l , C N) or n e utra l m o lec ul es h a ving lon e pa ir of e lec tron s (H 2 O, NH 1 ) .
(ii) Th e m e t a l ion n nd li ga nd s ac t as point c h a r g<' s h e n ce interac tion a mong th e m is pure ly e lec tros ta ti c .
(iii) The liga nd s wh e ~ a pp roac h to w a rds m e t a l a tom will not c om e (doubl e ). Th e e lec tron s o f m e ta l ato m a nd liga nd s
re pe l eac h 0 th e 1 whi c h d e s t. roy d ege n eracy o f 'd ' orbita ls a nd s plit th e m into two group s t 2 g and eg g roup s.
(crysta l fi e ld s plittin g). Th e diffe re n ce b e twee n e n e rgy le ve ls is call e d crys tal fi e ld s plittin g e n e rgy is re presente d
by 6. and a rbit ra rily t a k e n as IO Dq .
(iv) The e lec tro n of m etal a t o m occ upy th ese s plitte d 'd ' orbita ls accordin g to Hund 's rul e.
(vi As the ove rl a pping o f o rbi tals o f m e t a l a tom a nd ligand s is not involve d h e n ce c ova le nt c h a ra c te r does n't e xi s t in
complex.
(vii The s t a bili ty of co mple x d e p e nd s upon cry stal fill e d s tabilisation energy (CFSE) . High e r th e amount of C FSE,
m ore is s ta bili ty o f c ompl ex . Th e ga i n in e n e rgy a c hieve d by preferential filling of e lec tron s in o rbital s is c all e d
cry st a l fi e ld s t a bilisa tio n e n ergy (CFSE) .
(viii If CFSE val u e is zero , complex is unstable .
Application of CFT to Octahedral Complexes
In octahedral complex, the m e tal atom lie s at centre while six ligands occupy the X

vertices of regular o c tahedron a s follows:

Whe n ligands a pproach toward m e tal atom the five degenerate cl-orbitals lose their
d egen e r acy and s plit into two groups ½g and e g .
z z
The lig group con tai n d ")'' '½z and d x, orbitals while eg group contain d x2 _ Y 2 and d 2 2
o rbi t al s .
• Due t o greate r re pul s io n e g group orbital s h a s hig her energy than tig group orbitals . x'
• The diffe re n ce in e n e r gy levels b etwee n two s e ts is 6. 0 or I 0Dq (0 for octahedral
geometry).

,,
,, ,, ,,
,, ,, ,,
,,",,
/~ ~~--------- ---------
/
/ D egenerate 'd' orbitals ................ .... L\o = 0.4 Dq
~ / ofmeta lionin ' , , ....
~ crystal field
Degenerate ' d ' orbital s
of m etal/ion Splitting of 'd' orbitals
(Absence of ligands) in octahedral crystal field
• The ½g h as less e n e r gy by a n amount 0.4 6. 0 or 4Dq while eg has higher amount of energy by 0 .6 6. 0 or 6Dq than
dege n era te o rbi tals in crysta l fi e ld. The electron entering in t 2 g orbitals stabilies complex by 0.4 6. 0 or 4Dq a nd
electron e nte ri ng in e g orb it al d est a bilizes complex by 0 .6 6 0 or 6Dq .
• Th e en e r gy gain is o b tain e d by pre fe re ntial filling of electrons in orbitals whic h is called crystal field stabilisa tion
en ergy (C F SEI.
• In s tron g ligand fie ld 6 0 is hi g h whil e in w eak ligand fie ld 6. 0 is less .
• Spectrochemical series: De p e nding upo n the power of splitting of 'd' orbitals , the common li gands a r e arrange d
in ord e r of th e ir d ecr easin g fi e ld s tre n g th calle d spectrochemical series . The dec reasing fi e ld stre ngth is as
follow s CO > NH > e n > NH > E DTA > NCS > H O > C 2O4 2 > OH- > F- > s- > er > SCN- > Br > 1- .. ....
2
3 2

Tetrahedral Complexes I
In te trahedral compl e xes, th e m e t a l is place d a t centre of t e tra h e dron a nd four liga nds a re placed a t four c orners
of tetra h edron as foll ow s:
 Uttam 's MHT-C£r .
404 (Chern
41~,

,,------1-~---- '
z' 0/ -~---- ------/ j,-- Y'
I

'
.
I
I

I'
v ·
M'
\
~

-t--+- z
'' ''
I

. .
I I
:

y ' ------ ---,---/

:,,' :,,'
'<- --- - --- - - -- -•
x'
. d . to,va i·ds th e metal atom the t 2 orbitals h as greater repulsion by ligands than e O b
• W h en l1gan s a ppt oac 11 · g . g r llah
d nd d orbitals h ave hi gh er energy and d x2 _y2 , d 2 2 orbitals have lower energy.
d
thus xv' ,.2 a xz d rl ,1 (t )
•Y' 'Yl' "'x z '2g
,,,
,,, ,,, ,,,
,,,/ 0.4 Dq
,~ :~------------------
/ '
/ Degenerate 'd' orbitals ',, 0.6Dq
~ / of metal ion in ',,,
~ crystalficld ,
Degenerate ' d' orbitals '
of metal/ion
d,, _ Y'' d2 , ( eg)
(in absence of ligands)
Splitting of 'd' orbitals
in octahedral crystal field
The ½g orbitals has higher energy by 4Dq where as eg orbitals has lower energy by 6Dq than hypothetica
\ degenerate 'd ' orbitals in crystal field .
I• Each election entering in lower energy eg orbitals stabilises complex by 6Dq while electron entering in high
energy t 2g orbital destabilizes complex by 4Dq.
In strong ligand field electrons get paired in lower energy level (eg) forming low spin complexes while in weak
ligand field electron enter in higher energy level (t 2 g) forming high spin complexes.

Colours in Coordination Compounds

The colour of coordination compounds is due to d-d transition of electron and can be explained on basis oi
crystal field theory .
• According to this theory , the difference between the two sets of 'd' orbitals is very small. The electrons occupying
lower energy orbitals can be excited to higher energy orbitals with absorption of low energy radiation from visibk
region . As a result the transmitted light is coloured with complementary colour to the colour of light absorbed-
2
• Hydrate of cu• i.e. [Cu(H 2 0)i• absorbs light in red region of spectrum hence CuSO 4 solution is blue.
d,,.2-f:x)d 2 2 dx2_ ~ d 22

Photon (hv)
~

CtCO
d xy'd yz' d xz d xy,d yz,d xz

• Th e energy of incoming photon is equal to crysta l field s plitting of d -d orbitals .

i. e. t:.. = hv
t:,_ = ht [·: I]
V =

Magnetic Properties [baaed on CFT]: .

Th e magnetic properties depend upon magnitude of crystal field splitting.
Hi gh s pin co mplexes are more paramagnetic than low spin complexes .
d I d2 d3 ds d9 d 10 have sam e distribution of electrons in high spin a nd low spin complexes.
• Li~ibti~n•' of
(i)
CFT:
CFT expla in electros tatic interaction between metal ion and 'd ' orbitals but could not explain a~
ut 5 and? ! I
L. orbitals . \
I
 ..,·,,ation ( 'ompound1·
( oOlt I
405
;--
) It co uld not explain~ ~f - --.- - - - - __ _
( . covdknt chnra ct . O f . - - - - - - ---·-
(iii) It could not expla in a bout n bonct · . - er me ta l ligand honrl .
mg 111 cumpl exe ,
superiority CFT over VBT: s.
The stability and geom e try of co m 1.•
(i) . p exes ca n be ex pl· . d . V

The magnetic prope rties ca n be e 1 .

(ii) . a m e with Cl• r.
xp amed with CFT
(iii)
The co lour of comp lexes and d -d tra , -1. .
. .
·
ns1 1011 can be expl •. j . h
explain kine tic and thermodyna mi c ro . . , .
(iv) . ame< wit CFT.
!'-!!! . •
~ Bonding in Metal Carbonyl /
-
p pet tics of some complexes whi ch VBT
- · ·
•
The complexes whi c h conta in on ly co 1· ct
igan s arc ca ll e d h omo1eptic carbonyls. These carbonyls ha ve
particular geometry.
e.g. Fe(CO) 5 - Trigonal bipyramidal, Cr(CO) : octah edra l,
6 Mn(CO)s: Square pyramidal , Ni(CO) 1 - Tetrah ed ral
co co
I oc "--- I / co oc "" lo
Ni Cr
co/ \ "'co oc / / "---co / Fje - co
co co oc
(Tetrahedral) (Octahedral) T . _co .
ln metal carbonyls metal -ca rbon bond is CJ bond for ( ng~nal bipyra1:11idal)
vacant orbital of metal . med by donating lone pa1r of electrons by carbonyl carbon to
The donation of electron pair from filled 'd' orbi'tal 0f metal into empty antibonding orbital of CO lend s to
formation of metal -carbon n bond.

Stability of Coordination Compounds /

Using stability ~onstant _the stability of coordination compounds in solution can be determined. If the interaction
between metal 1011 and ligands is strong the complex is more stable and vice versa.
The equilibrium between metal ion and ligands is
M+a + nL-x ~ [MLnr b
M••: Metal ion (Lewis acid/ Electron pair acceptor)
L-1 : Ligand (Lewis base/ Electron pair donor)
[MLnrb: Complex where, a, x, b are the charges
The equilibrium constant (stability consta nt) is given by K.
[MLntb
K
[M +a ] [L- x ]b
It value of stability constant (K) is higher then greater is thermodynamic stability of a complex in the solution.

Factors affecting Stability of Complexes

Thermodynamic stability of complex depends upon-
(a) Charge density on metal ion:

Charge densi ty is ratio of ch arge and radius of ion i.e. ( Ch~rge )

radms
More the charge density on metal ion (Higher charge / smaller ionic size) greater is stability of complex.
The stability of complexe s of divalent metal ion s with same ligand is in the order
cu• 2 > Ni ' 2 > Co' 2 > Fe' 2 > Mn +2 > Cd +2 (Irving William order of stability)
(b) Nature of ligands:
In formation of complexes liga nd s act as Lewis bases [Electron pair donor] hen ce stabi lity of complex depends
upon basic strength of ligan ds more is the basic strength of liga nd , greater is stability of complex .
Application of Coordination Compounds
(1) Extraction of metal: The formation of complexes is used in ex traction of meta ls lik e Ag, Au etc.
Ag2 S + 4Na CN ~ 2Na[Ag(CNb] + N32S
2 Na[Ag(CNb ] + Zn ~ Na 2 [Zn(CN) 4 ] + 2Agt
Sodium dicyanoargentate (I) Sodium tetra cya no zincate (II)
(2) Qualitative and quantitative analysis: Complex formation is used in qualitative detec tion and quantitative
estimation of metal ions.
(A) Qualitative Analysis:
Cd' 2 in resence o ·eu. •2 :
 406
Ullam 's MHT-CET (Ch
€fr11J1n,
, I

The solution containing Cd +2 a nd Cu 2 • treated with excess of KCN

2
Cu "' + 4CW 0 /Cu(CN) 4 r 2

Cd -+ 2 + 4CW ~ [Cu(CN) 4 r
2
cyano complexes
/Cu(CNJ 4 r 2 being more stable than [Cd(CN) 4 r 2
, on passing H 2 S only CdS is precipitated .
(ii) Group I (Detection of Ag+):
If precipitate containing AgCl, Hg2 Cl 2 and PbC1 2 is treated with aqueous solution of ammonia the
AgCI forms a complex with ammonia and dissolves in solution while Hg2 C1 2 and PbC½ don 't , n
1onn
complexes and remain undissolved in the solution.
AgCl + 2NH3 ~ /Ag(NH 3 b ]C1
Complex
(B) Quantitative Analysis: Nickel can be detected and estimated by treating with dimethyl glyoxime to form
red precipitate of complex.
(3) Biological importance: The complex compounds play an important role in processes occurring in plants and
animals.

~
e.g. haemoglobin in blood is iron complex while vitamin B 12 is cobalt complex.
(4) In medicine: The complex compounds are used in medicine.
I e.g. platinum complex Cisplatin used in cancer treatment, EDTA used for lead poisoning.
(5) Electroplating of metals: Complex compounds are used in electroplating of noble metals like Au , Ag e.g. Gold
and silver can be electroplated from the complexes K[Ag(CNb] and K/Au(CNb]
Estimating hardness of water: EDTA (Hexadentate ligand) forms stable complexes with Ca +2 and Mg+2 . It can
(6)
be used for estimating hardness of water by a volumetric method. Since stability constants of Ca +2 and M{
complexes are different, selective estimation of ions is possible .
(7) Modifying the redox behaviour of metal ions: Cobalt can be be oxidised from +2 to +3 in presence of ligands ,
which is used by enzymes containing metal ions (Mo , Fe, Cu used in catalysed biological reactions) .
(8) Catalysts: Complex compounds are used as a catalyst in many reactions
e.g. Olefin into alcohol using Co(CO) 8 catalyst
Hydrogenation of alkene using Wilkinson catalyst (Ph 3 P) 3 RhC1. Ethylene and propylene into polyethene using
complexes of Ti and Al. Zi egler- Natta catalyst i s TiC1 4 + (C 2 H 5 ) 3 Al OR (CH 3 bA1.

000