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[180]
Coordination Compounds
Introduction: The complexes show a wide variety of physical and chemical properties which are quite different
from normal salts. These difference arise due to the difference in their structures.
Molecular or addition compounds: When solution containing two or more salts in stoichiometric (i.e.,
simple molecular) proportions are allowed to evaporate, we get crystals of compounds known as molecular or
addition compounds.
2 2 2 2
(carnallite)
KCl MgCl 6H O KCl.MgCl .6H O - -
2 4 2 4 3 2 2 4 2 4 3 2
(potash alum)
K SO Al (SO ) 24H O K SO .Al (SO ) .24H O - -
2 2
(potassium ferrocyanide)
Fe(CN) 4KCN Fe(CN) .4KCN -
These are of two types depending on their behaviour in aqueous solution.
I) Double salts or Lattice compounds: The addition compounds having the following characteristic are called
double salts or lattice compounds.
a) They exist as such in crystalline state.
b) When dissolved in water, these dissociate into ions in the same way in which the individual components
of the double salts do.
2 2
4 4 2 4 2 4 4
Mohr 's salt
FeSO .(NH ) SO .6H O Fe (aq) 2NH (aq) 2SO (aq)
- -
- -
3 2
2 4 2 4 3 2 4
Potash alum
K SO .Al (SO ) .24H O 2K (aq) 2Al (aq) 4SO (aq)
- -
- -
.II) Coordination (or complex) compounds: It has been observed that when solutions of Fe(
2
CN) and KCN
are mixed together and evaporated, potassium ferrocyanide,
2
Fe(CN) .4KCNis obtained which in aqueous
solution does not give test for the
2
Fe
-
and
CN
ions, but gives the test for
K
-
ion and ferrocyanide ion,
4
6
Fe(CN)
-
4
2 2 6
Fe(CN) 4KCN Fe(CN) .4KCN 4K Fe(CN)
-
- = -
Thus we see that in the molecular compound like
2
Fe(CN) 4KCN, the individual compounds lose their identity.
Such molecular compounds are called coordination (or complex) compounds.
A complex compound may contain a simple cation and a complex anion or a complex cation and a
simple anion or a complex cation and complex anion, e.g.
IV IV
2 6 3 4 2 2
K [Pt Cl ], [Pt (NH ) Br ]Br and
III III
3 6 2 4 3
[CO (NH ) ][Cr (C O ) ] are all complex compounds. The term complex compound is used
synonymously with the term coordination compound. In the above complex compounds, the ions
[ ] ,[ ( ) ] ,[ ( ) ]
- - IV 2 IV 2 III 3
4 3 4 2 3 6
Pt Cl Pt NH Br Co NH and
[ ( ) ]
III 3
2 4 3
Cr C O are called complex ions. Thus
a complex ion is an electrically charged radical which is formed by the union of a metal cation with one or more
neutral molecules or anions. Neutral complexes such as ( ) ( ) ( )
3 3
4 6 3
, , Ni CO Cr CO Co NH Cl
are
also known.
CO-ORDINATION COMPOUND
CO-ORDINATION COMPOUND
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[181]
Different parts of Co-ordination compound :
COORDINATION SPHERE
Aggregate of metal and ligands attached to it is called coordination sphere. It remains as a single unit in the
solutions. Metal atom acts as Lewis acid and ligand acts as Lewis base in these complexes.
e.g. K
4
[Fe(CN)
6
]
Ionic Co-oridnation
Sphere sphere
COORDINATION NUMBER
The number of lone pairs accepted by a given central atom from ligands. It may be different from number of
ligands attached.
In [Cu(NH
3
)
4
]
+2
the co-ordination no. of Cu is 4.
In [Co(en)
3
]
3+
, the co-ordination no. of cobalt is 6 and en is a bidentate ligand.
LIGANDS:
1. The neutral molecules, anions or cations which are directly linked with central metal atom or ion in a
complex ion are called ligands.
2. The ligands are attached to central metal ion or atom through co-ordinate bond or dative bond.
3. Denticity:The number of atoms (Sites) through which any ligand can attach to a metal atom is called its
denticity.
Type of Ligand Definition
Monodentate Ligands having only one site of attachement
Multidentate Ligands having many sites (atoms) through which these can attach to central
metal atom
Ambidentate Ligands which can attach a metal atom through more than one way /atom.
Bridging Ligands Ligands which can be attached simultaneously to more than one metal atoms.
(denoted by
in normenclature)
4. Classification of Ligands:
1) Neutral unidentate :
2) Univalent unidentate : , , , , , F Cl Br I OH CN
- - - - - -
3) Neutral bidentate : , , en bipy phen
4) Univalent bidentate : acac, DMG, Glycine
5) Bivalent bidentate : Oxalate, Sulphate, Carbonate
6) Multidentate or Flexidentate : Dien, Tren, EDTA
7) Ambidentate :
2
, , NCS NO CN
- - -
8) Bridging :
2
, , , , Cl OH NH CO NCS
- - - -
5. SOME COMMON POLYDENTATE LIGANDS
NAME ABBREVIATION STRUCTURE
Ethylenediamine en
H
2
N
NH
2
CO-ORDINATION COMPOUND
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[182]
2,2-bipyridyl bipy
N N
1,10-phenanthroline(phen phen
N N
Acetylacetanato Acac
Oxalate Ox
OOC COO
Glycinato gly
O
O
NH
2
Dimethylglyoximate DMG
C
C
N
N
C H
3
C H
3
O
OH
Diethylenetriamine dien
N H
2
NH
NH
2
Triethylenetetramine tren
H
2
N CH
2
CH
2
NH
CH
2
CH
2
NH CH
2
CH
2
NH
2
Ethylendiamine tetraacetate E.D.T.A.
N CH
2
CH
2
N
CH
2
COO
CH
2
COO
OOCH
2
C
OOCH
2
C
(Hexadentate)
6. Chelation
Polydentate ligands whose structure permit the attachment of their two or more donor atoms (or sites) to the
same metal ion simultaneously and thus produce one or more rings are called chelate or chelating ligands
(from the Greek for claw) or chelating groups. However, it should be noted that every multidentate ligand is not
necessarily a chelating ligand the coordinating atoms of the ligand may be so arranged that they cannot be
coordinated to the same metal atom to produce a ring structure. Thus
2 2 2 2
NH CH CH NH is a
chelating ligand, while
CO-ORDINATION COMPOUND
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[183]
2 2 2
N CH CH NH
2 2
(CH )
2 2
(CH )
is not, although both are diamines. The formation of such rings is termed chelation
and the resulting ring structures have been called chelate rings or chelates.
The chelate rings are most stable, because of reducd strain, when they have 5 or 6 membered ring including
the metal ion. The enhanced stability of complexes containing chelated ligands (i.e., multidentate ligands) is
known as the chelate effect.
( ) ( )
2 2
2 3 3 2
4 4
4 4 Cd H O NH Cd NH H O
- -
- -
...............(1)
0 1 0 1 1 0
56.3 , 67.3 , 37.2 / H k J mol S J mol K G kJ mol
- - -
A - A - A -
( ) ( )
2 2
2 2
4 2
2 4 Cd H O en Cd en H O
- -
- -
.....................(2)
0 1 0 1 1 0
56.8 , 14.1 , 60.7 / H kJ mol S J mol K G kJ mol
- - -
A - A - A -
Note that
0
H A
is same due to formation of Cd - N bond. There is difference in entropy. It is called Entropy
effect. In second case, 2en replace
2
4H O molecules. So increase in entropy of the system.
[ ( ) ]
3
2 3 2
Ag S O is called dithiosulphato S-argentate(I)
ion.
SCN
-
-
thiocyanato
CN
-
-
- : Cyano
2
NO
-
- nitro
NCS
-
-
isothiocyanato
NC
-
-
: Isocyano
ONO
-
-
nitrito
11. Naming of Bridging ligands: A bridging group is indicated by putting the Greek letter immediately
before i ts name and separated by hyphens from other l i gands. For
example, ( ) ( )
4
OH
2 OH 2
4 4
H O Fe Fe H O
-
< >
is called
Isomerism
Compounds that have the same chemical formula but different structural arrangement are called isomers.
Because of the complicated formula of many coordination compounds,the variety of bond types and the no of
shapes possible, many different types of isomerism occur.
Structural Isomersim
i) Polymerization Isomerism: This is not true isomerism because it occurs between compounds having
the same empirical formula, but different molecular weights. For example, , [Pt(NH
3
)
2
Cl
2
], [Pt(NH
3
)
4
][PtCl
4
],
[Pt(NH
3
)
4
]
[Pt(NH
3
)Cl
3
]
2
.
ii) Ionization Isomerism: This type of isomerism is due to the exchange of groups between the complex
ion and the ions outside it. [Co(NH
3
)
5
Br]SO
4
is red violet. An aqueous solution gives a white precipitate
of BaSO
4
with BaCl
2
solution, thus confirming the presence of free
2
4
SO
-
ions. In contrast [Co(NH
3
)
5
SO
4
]Br
is red. A solution of this complex does not give a positive sulphate test with BaCl
2
. It gives a pale yellow
coloured precipitate of AgBr with AgNO
3
, thus confirming the presence of free Br
ions.
iii) Hydrate Isomerism: Three isomers of CrCl
3
.6H
2
O are known. From conductivity measurements and
quantitative precipitation of the ionized chlorine, they have been given the following formulae:
Complex Colour No.of
3
AgNO Conc. Molar Cation
Cl
-
2 4
H SO cond. Exchange
[Cr(H
2
O)
6
]Cl
3
violet 3 100% No wt.loss 430 3HCl
[Cr(H
2
O)
5
Cl]Cl
2
.H
2
O green 2 66.66% 1
2
H O loss 220 2HCl
[Cr(H
2
O)
4
Cl
2
].Cl.2H
2
O dark green 1 33.33%
2
2H O loss 80 1HCl
a) Conc.
2 4
H SO removes lattice water and not the coordinated water molecules.
b) Molar conductivity is in
1 2 1
Ohm cm mol
- -
CO-ORDINATION COMPOUND
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[185]
c) When the known amount of the complex is sent through cation exchange resin ( )
3
RSO H , HCl is
liberated. The acid can be estimated by titration with standard NaOH solution.
Eg:- The first complex gives 3 moles of HCl per mole of the complex.
iv) Linkage Isomerism: Certain ligands contain more than one atom which could donate an electron pair.
In the
2
NO
-
ion, either N or O atoms could act as the electron pair donor. Thus there is the possibility
of isomerism. Two different complexes [Co(NH
3
)
5
(NO
2
)]Cl
2
and [Co(NH
3
)
5
(ONO)]Cl
2
have been prepared,
each containing the
2
NO
-
group in the complex ion.
v) Coordination Isomerism: If the complex is a salt having both cation and anion as complex ions then
the ligands can exchange position between the cation and the anion. This will result in the formation of
coordination isomers. For example
( ) ( ) ( ) ( )
3 3
6 6 6 6
Cr NH Co CN and Co NH Cr CN
( ) [ ] ( ) [ ]
3 4 3 4
4 4
Pt NH CuCl and Cu NH PtCl
3 2 4 3 2 2 4 2 4 2
[Co(en) ][Cr(C O ) ] and [Co(en) (C O )][Cr(en)(C O ) ]
2 2 4 2 4 2 3 2 4 3
[Cr(en) (C O )][Co(en)(C O ) ] and [Cr(en) ][Co(C O ) ]
vi) Coordination Position Isomerism: If in a multinuclear complex the distribution of ligands around the
metal centre changes, it results in a different isomer. Such an isomerism is called coordination position
isomerism. Some typical examples are
:
3 4 3 2 2 2 3 3 3 3 2
[(NH ) Co Co(NH ) Cl ] Cl and [Cl(NH ) Co Co(NH ) Cl]Cl < > < >
2
2
NH
O
2
2
NH
O
3 2 2 3 3
[(R P) Pt PtCl ] and [Cl(R P) Pt Pt(R P)Cl] < > < >
Cl
Cl
Cl
Cl
, (
3
R P Tri alkyl phosphine)
viii) Electronic Isomerism: The complex
3 5 2
[Co(NH ) NO]Cl exists in two forms. One is black
paramagnetic while the other is pink and diamagnetic. The black isomer is a Co(II) complex containing
neutral NO group whereas the pink one is a Co(III) complex with
NO
. This kind of isomerism is known
as electronic isomerism.
Stereo Isomerisms: Stereoisomers have the same bonds but the arrangement of atoms in space is different.
Stereoisomerism can be divided into two kinds: geometrical and optical.
i) Geometrical isomerism or cis-trans isomerism: It occurs when ligands can assume different positions
around rigid bonds with the metal ion.
(1) The compound [
3 2 2
Pt(NH ) Cl ]has a square planar structure. The two possible arrangements are.
Pt
3
H N
3
H N Cl
Cl
Pt
3
H N
3
NH
Cl
Cl
They are differentiated by dipole moment. Cis has larger dipole moment than trans one.For square
planar complexes
4 3
Ma , Ma b or
3
Mab where a and b are monodentate ligands, the geometrical
i someri sm i s not possi bl e. The square pl anar compl exes,
2 2
Ma b
2
Ma bc, Mabcd and
2
M(AA) ,
2
M(AB) where AA and AB represent symmetrical and unsymmetrical chelating ligands
give geometrical isomers.
(2) Geometrical Isomers - structures:
(a)
2 2
Ma b
3 2 2
Pt(NH ) Cl
CO-ORDINATION COMPOUND
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[186]
Pt
3
H N
3
H N Cl
Cl
Pt
3
H N
3
NH
Cl
Cl
(b)
2
Ma bc
( ) ( )
3 2
Pt(NH ) Cl Br
Pt
3
H N
3
H N Br
Cl
Pt
3
H N
3
NH
Br
Cl
(c) Mabcd [ ]
3 5 5
Pt(NH )(C H N)(Cl)(Br)
Pt
3
H N
Br Cl
Pt
3
H N 5 5
NC H
Cl
5 5
NC H
Br
Pt
3
H N
5 5
NC H
Cl
Br
(d) Bridged binuclear planar complexes like
[ ( ) ]
3 2 2
Pt PEt Cl may exist in three isomeric forms:
Cl
Pt
Cl
Pt
PEt
3
Et
3
P Cl Cl
Cl
Pt
Cl
Pt
Cl
Et
3
P Cl PEt
3
Et
3
P
Pt
Cl
Pt
Cl
Et
3
P Cl Cl
trans
cis unsymmetrical
ii) (1) Six coordinated octahedral complexs of the type , , , ,
4 2 3 3 3 2 3 2 2
Ma b Ma b Ma b c Ma bcd Ma b cd
,
2
Ma bcde Mabcdef would all give geometrical isomers. Systems with one or two bidentate ligands
and rest monodentate would also give geometrical isomers.
(2) A number of isomers are possible whether they can be isolated or separated is a different question
which depends on so many factors. As we increase the number of different ligands, the possible number
of isomers increases.
(3)
4 2
Ma b type of complex would give only two isomers cisand trans.
CO-ORDINATION COMPOUND
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[187]
(4)
3 3
Ma b gives two isomers facial (fac) and meridional (mer) isomers. In the former (fac) three ligands
of one type form one triangular face of the octahedron and the other three on the opposite face. In the
latter (mer) one set of these ligands are arranged around an edge of the octahedron whereas the other
set occupies the opposite edge as shown in figure.
M
a
a b
b
b
a
M
a b
b
a
b
a
Facial and meridional isomers of
3 3
Ma b complex
(5) Mabcdef is expected to give 15 isomers. ( )
2
6 C . a to f are unidentate ligands.
iii) Optical isomerism:
(1) Two isomers which have almost identical physical and chemical properties like mp, bp, density, colour
etc., but differ in the way they rotate the plane-polarised light are called optical isomers.
(2) Optically active compounds exist in pairs and are known as stereoisomers or enantiomers. These
isomers aer non-superimposable mirror images of each other.
(3) Any molecule which contains either a centre of symmetry or a plane of symmetry will not show optical
isomerism.
(4) Optical isomerism is rarely observed in square planar complexes. Tetrahedral complexes of the
type[ ( ) ]
2
M AB [AB = bidentate ligand] do give optical isomers as shown in figure especially where M
= Be, B etc.
M
A
B
A
B
M
A
B
A
B
\
(5) (a) Optical isomerism is very common with octahedral complexes.
(b) But , , , ( ) , ( ) , ( ) ,
5 4 2 3 3 3 2 2 2
Ma b Ma b Ma b M AA M AA ab M AA a b ( )( )
2
M AA BB a ,do not
show optical isomerism since they have symmetry element.
(c) A few typical examples which show optical activity are
CO-ORDINATION COMPOUND
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[188]
( ) ( ) ( ) ( )
3 2 3 3
2 4 2 4 2 4 2 4
3 3 3 3
, , , ( ) Co en Ir C O Cr C O Al C O C O Oxalate
- - - -
Co
2
H N
2
H N
2
H N
2
H N
2
H C
2
H C
2
CH
2
CH
2
CH
2
CH
Co
N
2
NO
2
NO
N
N
N
en
en
Co
N
2
O N
2
O N
N
N
N
en
en
Co
2
H N
2
NH
2
H C
2
H C
2
CH
2
CH
2
CH
2
CH
3 - 3 -
- -
2
NH
2
NH
2
H N
2
H N
2
NH
2
NH
(d)
( ) ( )
( )
2 2 2 2
.
sin .
Co en NO and Cis Co en Cl are optically active
Trans isomer is not optically active ce it has symmetry element Not unsymmetrical
Cis
- -
-
-
Illustration 5: How do you distinguish between the following pairs of isomers?
i) [ ( ) ] [ ( ) ]B
3 5 3 5
Cr NH Br Cl and Cr NH Cl r
ii) ( ) ( ) ( ) ( )
2 2 2 2 3
4 6
.2 Co H O Cl Cl H O A and Co H O Cl B
Solution:
i) The isomers can be distinguished by using
3
AgNO reagent. One gives curdy precipitate of AgCl
soluble in ammonia while the other will form light yellow precipitate of AgBr partially soluble in
ammonia.
ii) A B
3
AgNO
1 mol of AgCl 3 mol of AgCl
Molar Conductivity 60 420
1 2 1
( ) Ohm cm mol
- -
Wt.Loss on Conc.
2 4
H SO Loss of
2
2H O No wt.loss
Cation exchange resin 1 mol of HCl 3 mol of HCl
( )
3
RSO H
[( ( ) ] ( )
III 3
3 6 3
Co NH Cl
-
Co
H
3
N
H
2
O
Cl
NH
3
NH
3
Cl
Cl
NH
3
NH
3
.
3 3 2
CoCl 5NH H O or
[( ( ) ( )] ( )
III 3
3 5 2 3
Co NH H O Cl
-
.
3 3
CoCl 5NH or
Co
H
3
N
H
3
N
Cl
NH
3
Cl
NH
3
NH
3
Cl
[( ( ) ] ( )
III 2
3 5 2
Co NH Cl Cl
-
.
3 3 2
CoCl 4 NH H O or
[( ( ) ]
III
3 4 2
Co NH Cl Cl
-
Co
H
3
N
H
3
N
Cl
Cl
NH
3
Cl
NH
3
. [ ( ) ]
III 0
3 3 3 3 3
CoCl 3NH or Co NH Cl
Co
H
3
N
Cl
Cl
NH
3
Cl
NH
3
ii) Every element tends to satisfy both its primary and secondary valencies. In order to meet this requirement
a negative ion may often show a dual behaviour, i.e. it may satisfy both primary and secondary valencies
since in every case the fulfillment of coordination number of the central metal ion appears essential .
iii) Basis of Werners theory: Different isomers, color of the complexes, precipitation, electrical conductivity,
Ion exchange studies, dipole moment, dehydration temperature.
Characteristic of Co(III) ammines
Ammines (i.e. No. of Cl
)
3
CoCl
3
.
5NH
3
. H
2
O 3 (100%) 430 4 (3+,1-) [Co
III
(NH
3
)
5
(H
2
O)]
3+
(Cl
)
CoCl
3
.5NH
3
2(66.66%) 250 3 (2+,-1) [Co
III
(NH
3
)
5
Cl]
2+
+(Cl
)
CoCl
3
.4NH
3
1(33.33%) 100 2 (1+,1-) [Co
III
(NH
3
)
4
Cl
2
]+Cl
CoCl
3
. 3NH
3
0 ( -- ) 0 - - [Co
III
(NH
3
)
3
Cl
3
]
10
(non-electrolyte)
ion is a weak field ligand it is unable to pair the unpaired electrons and hence, the Cl
F
is a weak ligand hence six lone pairs of six
F
are filled in outer d-orbitals of
3
Co
-
which has now four electrons unpaired. Thus
3
6
CoF has
3 2
sp d hybridization
in
3
Co
-
and is thus paramagnetic due to unpaired electrons.
FAILURE OF VB THEORY:
(a) Pauling VB theory could not explain satisfactorily the geometry of ( )
2
3
4
Cu NH
-
.
2 9
3 Cu d -
( )
2
3
4
: Cu NH
-
3
sp hybridization, Tetrahedral. But the actual geometry (experimentally) is found to be square
planar. This was explained as
( )
2
3
4
: Cu NH
-
(b) It could not explain the color of the complexes.
CO-ORDINATION COMPOUND
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9837617412
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[194]
(c) It could not explain why certain ligands act as strong field ligands and others as weak field ligand.
Table: Hybridization and Geometry of the complexes:
Coordination
No.
Hybridization Geometry Examples
2 Sp Linear
( ) ( )
1
3
2 2
Ag NH Ag CN
- -
( ) ( )
1
3
2 2
, Cu NH Cu CN
- -
( ) ( )
1
3
2 2
, Au CN Au NH
- -
3
(rare)
2
Sp
Trigonal
planar
[ ]
1
3
HgI
-
4
3
Sp
Tetrahedral
2 1
4 4 4
, , BeCl AlCl FeCl
- - -
,
( ) ( )
2
4
, , , CoX X Cl Br I NCS
-
[ ] ( )
2
4
, , , ZnX X Cl Br I NCS
-
[ ] ( )
2
4
, , , CdX X Cl Br I NCS
-
[ ] ( )
2
4
, , , HgX X Cl Br I NCS
-
( )
2 2
4 4
4
, , MnCl MnBr Ni CO
- -
,
2 2 2
4 4 4
, , NICl SnCl GeCl
- - -
4
2
dsp
Square
planar
( ) ( )
2
4 2
, Ni CN Ni DMG
-
( ) DMG Dimethyl glyoxime ,
[ ]
2
4
( , , , , ) PtX X Cl Br I NCS CN
-
[ ] ( )
2
4
, , , , PdX X Cl Br I NCS CN
-
( ) ( )
2
3 2
2 2
, Pt NH Cl Pt en
-
5
(rare)
3
sp d
Trigonal
bipyramid
( )
5
Fe CO , ( )
4
3
Zn tu SO
2
4
Ctu Itiourea SO
-
is abidentate ligand)
5
(rare)
3
dsp
Square
pyramid
( )
3
5
Ni CN
-
6
2 3
d sp
Octahedral
( ) ( )
4 3
6 6
, Fe CN Fe CN
- -
( ) ( )
3 3
3
6 3
Co NH Co en
- -
( ) ( )
3 3
3
6 6
, Cr NH Cr CN
- -
6
3 2
Sp d
Octahedral
( )
3
2
6
Fe H O
-
, [ ]
3
6
FeF
-
, ( )
2
2
6
MN H O
-
( ) ( )
2 2
3 2
6 6
Ni NH Ni H O
- -
, ( )
2
3
Ni en
-
7,8,9,12
(rare)
[ ] ( ) ( )
3
3
7 2 2
9 12
, , ZrF Nd H O Lu H O
-
-
(1) Ligand Field Splitting in Octahedral Complex: Let us consider the case of six ligands forming an
octahedral complex. For convenience, we may regard the ligands as being symmetrically positioned along the
axes of a Cartesian co-ordinate system with the metal ion at the origin. To simplify the situation, we can
consider an octahedral complex as a cube, having the metal ion at the centre of the body and the 6 ligands at
the face centres
and if we take the metal ion as the origin of a Cartesian co-ordinate, the ligands will be along the axes. It is
obvious that not all of the orbitals will be affected to the same extent when the ligands approach the metal ion.
The orbitals lying along the axes
( )
2 2 2
z x y
d and d
-
will be more strongly repelled than the orbitals with lobes
directed between the axesd
xy
, d
xz
, d
yz
). The d-orbitals are thus split into two sets with the
2 2 2
z x y
d and d
at a
higher energy than the other three.
( )
2
y
2
x
2
z
d , d
-
d
xy
, d
yz
, d
xz
A
0
(2) Ligand Field Splitting in Square Planar Complex: If the central metal ion has eight
d-electrons( ( )
2
Ni
-
, these will be arranged as
In a weak octahedral ligand field, a regular octahedral complex is thus formed by using outer d-orbitals.However,
under the influence of a strong ligand field, the electrons in the 2
z
d and 2 2
x y
d
-
orbitals may pair up, leaving one
vacant d-orbital, which can accept a lone pair from a ligand. Consider an octahedral comple, when two ligands
in z - direction are removed, then a square planar complex results.
When the two axial ligands ( in z - direction) are removed. z containing orbitals will be come lower in energy
and xy containing orbitals will become higher in energy. 2 2
x y
d
-
orbital is involved in bonding. Strong field
ligands usually give rise to square planar complexes and are diamagnetic. 1.33
SP O
A A
Eg:- ( ) [ ] ( )
2 2
2
4 3
4 4
, , Ni CN PtCl Pt NH
- -
-
CO-ORDINATION COMPOUND
Delhi: 48, Hasanpur, I.P. Extn., Patparganj, Pin-110092; Ph: 011-43094712, Mobile:09811744029
Kashipur : Aryna Nagar, Near Himalyan Public School, Kashipur (Uttarakhand) Ph. : 05947-276252Mobile :
9837617412
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[198]
( )
2
4
Ni CN
-
is a square planar where as
2
4
NiCl
-
is tetrahedral since
CN
-
is a strong field ligand.
(3). Ligand Field Splitting in Tetrahedral Complexes: A regular tetrahedron is related to a cube with an
atom at the centre and four of the eight corners occupied by ligands.
y
x
z
The directions x,y and z point to the centre of the faces. The 2
Z
d and 2 2
x y
d
-
orbitals point along x,y and z axis
and d
xy
, d
yz
and d
xz
orbitals point in between x,y and z.The directions of approach of the ligands does not
coincide exactly with either the 2
z
d and 2 2
x y
d
-
orbitals (or) the d
xy
, d
yz
and d
xz
orbitals. The approach of ligands
raises the energy of both sets of orbitals, but since the d
xy
,d
yz
and d
xz
orbitals correspond more closely to the
position of the ligands, their energy increases most and the 2
Z
d and 2 2
x y
d
-
orbitals are filled first. This is
opposite to what happens in octahedral complexes.
O t
A < A and so many tetrahedral complexes are
paramagnetic and high spin complexes. ( )
4
0.45 ,
9
t O O SP O t
A A A A > A > A
.
Consider,
4
FeCl
-
, Ligand field theory :
3 5
: 3 Fe d
-
| | |
| |
( ) 5 5 2 35 5.87 . B M -
CO-ORDINATION COMPOUND
Delhi: 48, Hasanpur, I.P. Extn., Patparganj, Pin-110092; Ph: 011-43094712, Mobile:09811744029
Kashipur : Aryna Nagar, Near Himalyan Public School, Kashipur (Uttarakhand) Ph. : 05947-276252Mobile :
9837617412
E-mail: info@marksmanclasses.com Website: www.marksmanclasses.com
[199]
Metal Carbonyls
a) The homoleptic carbonyls (compounds containing carbonyl ligands only) are formed by most of the transition
metals. These carbonyls have simple, well defined structures. Tetracarbonylnickel (0) is tetrahedral,
pentacarbonyliron(0) is trigonal bipyramidal while hexacarbonylchrominum (0) is octahedral.
Decacarbonyldimanganese(0) is made up of two Mn(CO)
5
units joined by a Mn-Mn bond.
Octacarbonyldicobalt (0) has a Co-Co bond bridged by two CO groups
CO
NI
OC
CO
CO
Ni(CO)
4
Tetrahedral
CO
Fe
OC
OC
CO
CO
Fe(CO)
5
Trigonal bipyramidal
Cr
CO
CO
OC
OC CO
CO
Cr(CO)
6
Octahedral
Mn
CO
CO
OC Mn
OC CO
CO
CO
CO
OC CO
[Mn
2
(CO)
10
]
Co Co
CO OC
OC
OC
CO
CO
CO
CO
[Co
2
(CO)
8
]
(b) Bonding in metal carbonyls:
(a) o - donation
Empty Metal d - orbitals Filled CO orbitals
Filled CO orbitals overlap with empty metal d - orbitals.
(b) r - back bonding
Filled metal d - orbitals overlap with empty
*
r
molecular orbitals of CO.
CO-ORDINATION COMPOUND
Delhi: 48, Hasanpur, I.P. Extn., Patparganj, Pin-110092; Ph: 011-43094712, Mobile:09811744029
Kashipur : Aryna Nagar, Near Himalyan Public School, Kashipur (Uttarakhand) Ph. : 05947-276252Mobile :
9837617412
E-mail: info@marksmanclasses.com Website: www.marksmanclasses.com
[200]
(c) Resonance forms can be represented as
M C O M C O - =
The M - C bond order increases and bond length is expected to decrease. The C - O bond order
decreases and C - O bond length increases when compared to C - O bond length in uncoordinated
CO. More the back bonding the lesser will be C - O bond.
(d) The o - donation and r - bonding order and greater will be C - O bond length back bonding occurs
synergistically. Both occur simultaneously.
(e) Since r - back bonding requires filled metal d - orbitals, carbonyls are usually formed in lower
oxidation state.
( ) ( ) ( )
3
3
6 5 6
, Cr CO Fe CO Cr NH
-
is stable but
( )
3
6
Cr CO
-
is not known.
(f) Both CO and
2
N are isoelectronic (14e). But metal carbonyls are stable whereas metal dinitrogen
( ) M N N - = complexes are less stable. In metal carbonyls, the
*
r
molecular orbital is of lower
in energy and can overlap with metal d - orbitals. In
2
N , the
*
r
- molecular orbital energy lever is
higher and cannot overlap with the metal filled d- orbitals. No back donation possible in
2
N .
(g) Usually a ligand donate an electron pair to metal. In CO, it can accept electron from the metal. It is
known as r - acceptor ligand.
3
, , , CO CN NO PPh
- -
(Vacant d - orbital) can act as r - acceptor
ligands.
3 2
, NH H O are only o - donors and not r - acceptor.