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CO-ORDINATION COMPOUND

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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
µ
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.

IUPAC Nomenclature Of Coordination Compounds
1. Naming of salt: If the complex is a salt, the cation is named first followed by the name of the anion.
2. For the complex entity, the name of the ligand(s) is put before the name of the metal atom. However,
the reverse order is followed in writing the formula of the compound.
3. Naming of the negative ligands: The names of all anionic ligands end in ‘o’ .
2
: , : , : , : F Fluoro Cl Chloro O Oxo CN Cyano
- - - -
Cationic and neutral ligands have no special ending. There are a few exceptions like ‘aqua’ for H
2
O,
ammine for NH
3
, carbonyl for CO, and nitrosyl for NO groups.
4. Indication of the number of ligands: The number of ligands is indicated by adding prefixes di–, tri–,
tetra–, penta–, hexa–, etc. for two, three, four, five, six, etc entities of the ligand. For example,
3 6 3
[Co(NH ) ]Cl will be called hexaamminecobalt(III) chloride.
If the ligands are big complicated groups, instead of di–, tri–, tetra–, penta– prefixes we use bis–, tris–
, tetrakis–, pentakis– etc. For instance
3 3 2
Cu(CH COCHCOCH ) is called bis(acetylacetonato)
copper.(II)
5. Order of Naming ligands: The ligands are quoted in alphabetical order. Numerical prefixes indicating
the number of ligands are not considered in determining that order. For example, a compound like
2 2
[CoCl(NO )(en) ]Cl will be called chlorobis (ethylenediamine) nitrocobalt (III) chloride.
6. Oxidation state: The oxidation state of the metal ion in a complex is indicated by Roman (I), (II), (III)
etc. or an Arabic (O) and placed in parenthesis immediately after the name of the metal.
7. Naming of complex: The name of the complex anion ends in ‘ate’ and the Latin name of the metal
atom is used.
2 6
K [PtCl ] : Potassium hexachloroplatinate(IV),
2
K[Ag(CN) ] :Potassium
dicyanoargentate(I).
8. A little space is given between the name of the cation and the anion. No space or hyphen is used
anywhere else.
9. Once the complex entity is completely identified according to the above rules, no mention of the number
of cations or anions used for charge balancing is required. For example,
3 6 3
[Co(NH ) ]Cl is called
hexaamminecobalt(III) chloride and not hexaamminecobalt(III) trichloride. Similarly,
2 6
K [PtCl ] is named
potassium hexachloroplatinate(IV) and not dipotassium hexachloroplatinate(IV).
CO-ORDINATION COMPOUND
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[184]
10. Ligands having more than one donor atom: If a ligand has more than one donor atom, the actual
atom involved in the bond formation with the metal ion is indicated by putting italicized symbol of the
atom after the name of the ligand. For example,

[ ( ) ]
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 ‘ µ’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
µ
-dihydroxobis [tetraaquairon(II)] ion and the
formula could be written as
4
2 4 2 2 4
[(H O) Fe( OH) Fe(H O) ]
-
µ - also.
12. Structural information may be given in the names and formulae by prefixes such as cis–, trans– etc.
3 2 2
[Pt(NH ) Cl ]can be written as cis-dichlorodiammineplatinum(II) or trans-dichlorodiammineplatinum(II),
respectively.
Note: When writing the formula of a complex, the central atom is listed first. The coordinated groups (i.e., ligands)
are listed in the order: formally anionic ligands, neutral ligands followed by cationic ligands. Within each
group, the ligands are listed alphabetically according to the first symbol
Illustration 3: Write down IPUAC name of K
2
[Fe(CN)
3
Cl
2
(NH
3
)
2
]
Solution: The positive part is named first followed by the negative part. In the negative part the names are written
in alphabetical order followed by metal. So the name is Potassium diamminedichlorotricyano-N-ferrate
(III).
Illustration 4: Using IUPAC rules, write the formula for the following:Hexaamminecobalt(III) sulphate
Solution: [Co(NH
3
)
6
]
2
(SO
4
)
3

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 cis–and trans–.
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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
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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

Werner’s Theory Of Coordination Compounds(1893): Postulates
i) Most elements exhibt two types of valenceis: (a) primary valency and (b) secondary valency.
a) Primary valency: This corresponds to oxidation state of the metal ion. This is also called principal,
ionisable or ionic valency. It is satisfied by negative ions and its attachment with the central metal ion is
shown by dotted lines.
b) Secondary or auxiliary valency: It is also termed as coordination number (usually abbreviated as CN)
of the central metal ion. It is non-ionic or non-ionisable (i.e. coordinate covalent bond type). This is
satisfied by either negative ions or neutral molecules. The ligands which satisfy the coordination number
are directly attached to the metal atom or ion and shown by thick lines. While writing down the formulae
these are placed in the coordination sphere along with the metal ion. These are directed towards fixed
position in space about the central metal ion, e.g. six ligands are arranged at the six corners of a regular
octahedron with the metal ion at its centre. This postulate predicted the existence of different types of
isomerism in coordination complexes and after 19 years Werner actually succeeded in resolving various
CO-ORDINATION COMPOUND
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[189]
coordination examples into optically active isomers.
.
3 3
CoCl 6NH or
Co
H
3
N
H
3
N
Cl
NH
3
NH
3
Cl
Cl
NH
3
NH
3

[( ( ) ] ( )
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

ions Molar Total No. of Charge type Ionic
Complexes Precipitated conductivity ions given on ions Formulation
as AgCl by range by complex
AgNO
3
(Ohm
-1
cm
2
mol
-1
) in soln.
CoCl
3
.6NH
3
3(100%) 430 4 (3+,-1) [Co
III
(NH
3
)
6
]
3+
(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)

Effective Atomic Number: (EAN)
1) Sidgwick, with his effective atomic number rule, suggested that electron pairs from ligands were added
until the central metal was surrounded by the same number of electrons as the next noble gas.
2) [ ( ) ]
4 6
K Fe CN (potassium ferrocyanide): Fe
2+
; 24e
-

4–
6
[Fe(CN) ] = 24 (6 2) 36 - × · (Kr - The
nearest noble gas). The EAN rule correctly predicts the number of ligands in many complexes.
CO-ORDINATION COMPOUND
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[190]
3) Effective atomic numbers of some metals in complexes
Atom Atomic No. Complex Oxidation state Ligand Electrons EAN
Cr 24 [Cr(CO)
6
] 0 12 36
Fe 26 [Fe(CN)
6
]
4-
2 12 36
Fe 26 [Fe(CO)
5
] 0 10 36
Co 27 [Co(NH
3
)
6
]
3+
3 12 36 [Kr]
Ni 28 [Ni(CO)
4
] 0 8 36
Cu 29 [Cu(CN)
4
]
3-
1 8 36
Pd 46 [Pd(NH
3
)
6
]
4+
4 12 54 [Xe]
Pt 78 [Pt(Cl
6
)]
2-
4 12 86 [Rn]
Fe 26 [Fe(CN)
6
]
3-
3 12 35
Ni 28 [Ni(NH
3
)
6
]
2+
2 12 38
Pd 46 [PdCl
4
]
2-
2 8 52
Pt 78 [Pt(NH
3
)
4
]
2+
2 8 84
4) There are, however, a significant number of exceptions where the EAN is not found to have a noble gas
configuration.
a) ( )
4
: 27 4 2 35 Co CO - × · , In such cases the complex has odd electron. ( )
4
Co CO is
therefore unstable and dimerises to form ( )
2
8
Co CO .
b) ( )
5
: 25 5 2 35 Mn CO - × ·
( )
5
Mn CO is unstable and ( )
2
10
Mn CO is stable.
c) ( ) ( ) ( )
4
5
36 Co CO and Mn CO e Kr
- - -
- are stable as they obey EAN rule.
d) ( ) ( )
6 6
: 23 12 35 , V CO e V CO
- -
- · is stable. ( )
6
V CO does not dimerise as it has complete coordination
sphere (coordination no.6)
5) ( )
2
3
6
: 25 6 2 37 Co NH e
-
-
  - × ·
 
( )
3
3
6
: 24 6 2 36 Co NH e
-
-
  - × ·
 
( )
3
3
6
Co NH
-
 
 
is more stable than ( )
2
3
6
Co NH
-
 
 
.
( )
2
3
6
Co NH
-
 
 
can be easily oxidised by air
2
O to ( )
3
3
6
Co NH
-
 
 
.
6) NO is considered as
3e
-
donor.
3 2 CO NO =
From ( )
6
Cr CO , one can get ( ) ( ) ( )
3 2 4
Cr CO NO and Cr NO . No other complex can form.
( ) ( )
4
: 24 4 3 36 Cr NO Kr - × · .

Valence Bond Theory (Pauling)
1. Pauling used hybridization theory to derive the geometry of the complex. The basis of this theory is the
magnetic property of the complexes. He classified ligands into ‘Strong field’ (Low spin complexes) and ‘Weak
field’ (High spin complexes). The complexes can be diamagnetic or paramagnetic. If paramagnetic, the
magnetic moment ( ) 2 n n BM µ · - , n = no.of unpaired electrons.
CO-ORDINATION COMPOUND
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[191]
2. Strong field and weak field ligands:
(a) ( )
4
6
Fe CN
-
 
 
6 2 2 6
: 3 4 , : 3 Fe d s Fe d
-

2 3
d sp hybridization octahedral.
( ) Diamagnetic Experimentally shown
CN
-
is a SFL, Low spin complex
Inner orbital complex (uses inner 3d orbital)
(b)
( )
3
3 5
6
: : 3 Fe CN Fe d
-
-
 
 
( )
3
6
: Fe CN
-
 
 
2 3
d sp hybridization octahedral paramagnetic, low spin ( ) 1 2 3 1.73 BM µ · - · ·
CN
-
is a strong field ligand. Inner orbital complex.
( )
4
6
K Fe CN   .
 
is diamagnetic and ( )
3
6
K Fe CN  
 
is paramagnetic. Both of them can be
differentiated.
(c)
[ ]
3
3 5
6
, ; 3 FeF Fe d
-
-
3 2
sp d octahedral paramagnetic, HIgh spin complex. ( ) 5 5 2 35 5.87 BM µ · - · · outer
orbital complex (uses outer 4d orbitals) ( ) 5 5 2 35 5.87 BM µ · - · ·
Stereochemistry
(a) ( ) ( )
8 2
4
, ;3 4 Ni CO Ni O d s
(CO is a strong field ligand. The complex was found to be diamagnetic experimentally.)
CO-ORDINATION COMPOUND
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[192]
3
sp Hybridization Tetrahedral
(b)
[ ]
2
4
NICl
-
is found to be paramagnetic with a magnetic moment of 2.84 BM.
3
sp , tetrahedral.
(c) ( )
2
4
Ni CN
-
 
 
is found to be diamagnetic.
( )
2
4
: Ni CN
-
 
 
2
dsp sq.planar
(d)
( )
2
4
PtCl
-
is found to be diamagnetic.
2 8
: 5 Pt d
-
2
dsp
, square planar
Note that
2
4
NiCl
-
is paramagnetic but
2
4
PtCl
-
is diamagnetic. It is not that
Cl
-
is acting as weak or
strong field ligand. Its field strength does not change. But the 5d orbitals in Pt are more open, outer and
exposed,so it feels the
Cl
-
field strong and electrons pair up.
(e) [FeCl
4
]

. The electronic configuration of Fe
3+
ion is 3d
5
Since Cl

ion is a weak field ligand it is unable to pair the unpaired electrons and hence, the Cl

ion uses 4s and
4p orbitals to form a tetrahedral complex of sp
3
hybridisation.

Illustration-6: Calculate the magnetic moment of the “Brown ring” complex.
“Brownn ring” complex is ( ) ( )
2
2
5
Fe H O NO
-
 
 
, 1 2, 1 x O x - - · - · -
6 2 1 6 1
: 3 4 , : 3 4 Fe d s Fe d s
-
1
: Fe
-
( ) ( )
2
2
5
Fe H O NO
-
 
 
3 2
sp d , octahedral ‘outer orbital complex.
Paramagnetic, ( ) 3 3 2 15 3.87 BM µ · - · · .
Illustration-7:. All octahedral Ni(II) complexes are paramagnetic and outer orbital complexes. Explain.
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[193]
( )
2
2 8
3
6
, ; 3 Ni NH Ni d
-
-
 
 
( )
2
3
6
: Ni NH
-
 
 
3 2
, 2.84 sp d BM µ ·
On pairing up, we do not get
2 3
d sp . So no pairing up.
( )
2
2
6
Ni H O
-
 
 
3 2
, 2.84 sp d BM µ ·
Irrespective of whether the ligand is strong field or weak field ligand all the complexes are outer orbital and
paramagnetic.
Illustration 8:
3
3 6
[Co(NH ) ]
-
is diamagnetic and
3–
6
[CoF ] is strongly paramagnetic. Explain
Solution:
3
Co
-
3
3 6
[Co(NH ) ]
-
3–
6
[CoF ]
2 3
d sp
3 2
sp d
diamagnetic due to paired
electrons
Paramagnetic due to four unpaired electrons
3
Co
-
has
6
3d
configuration with four unpaired electrons in ground state. In presence of
3
NH (strong l i gand) al l the unpai red el ectrons i n
3
Co
-
get pai red and thus
3
3 6
[Co(NH ) ]
-
has
2 3
d sp hybridization (octahedral structure), thus it is diamagnetic (no electron unpaired).

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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[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
-
-
   
   


Ligand field theory
Shapes of d-Orbitals: Since d orbitals are often used in coordination complexes it is important to study their
shapes and distribution in space. The five d orbitals are not identical and the orbitals may be divided into two
sets. The three
2g
t orbitals have identical shape and point between the axes, x, y and z. The two
g
e orbitals
have different shapes and point along the axes. Alternative names for
2g
t and
g
e are
dr
and d¸ respectively.
CO-ORDINATION COMPOUND
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[195]
x
2g
t
orbitals
(d ) r
x y
y
z z
xy
d
xz
d
yz
d
+
-
+ -
-
+
+ -
-
+
+ -

(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


Outer orbital and Inner orbital complexes
a) In a weak ligand field such as [CoF
6
]
3–
, the approach of the ligand causes only a small split in the
energy level.
O
A < P(pairing energy)
CO-ORDINATION COMPOUND
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[196]
( ) 4 4 2 24 4.87 . B M µ · - · ·
Since the ligand is a weak field ligand, its repulsions with the electrons in 2 2 2
z x y
d and d
-
orbitals are very
less (or) in other words we can say that the electrons in 2
z
d and 2 2
x y
d
-
cannot move away from the
approaching ligands since they have insufficient energy to pair up with the electrons in d
xy
, d
yz
and d
xz
orbitals.
Thus there are no vacant orbitals in the 3d shell and the ligands occupy the first six vacant orbitals (one
4s, three 4p and two 4d). Since outer d orbitals are used, this is an outer orbital complex. The orbitals
are hybridised and are written sp
3
d
2
to denote this. Since none of the electrons has been forced to pair
off, this is a high spin complex and will be strongly paramagnetic because it contains 4 unpaired 3d
electrons.
(b) Under the influence of a strong ligand field as in the complex [Co(NH
3
)
6
]
3+
, the approach of the ligand
causes a greater split in the energy level.
0
A > P
Since, the split is very high, we can say that the energy difference between the two sets of orbitals is much
greater and this energy difference is sufficient to allow the electrons in 2 2 2
z x y
d and d
-
orbitals to move into the
half filled d
xz
, d
xy
and d
yz
orbitals, even though this pairing requires energy. We can also view this like, the ligand
repel the electrons in higher energy level to an extent such that they get paired up against Hund’s rule
The 2
z
d and 2 2
x y
d
-
orbitals become vacant. The six ligands each donate a lone pair to the first six vacant
orbitals, which are: two 3d, one 4s and three 4p. Inner d-orbitals are used and so this is an inner orbital
complex. The orbital are hybridised and written d
2
sp
3
to denote the use of inner orbitals.
Since, the orginal unpaired electrons have been forced to pair off, there is a low spin complex and is in fact
diamagnetic.
The inner and outer orbital complexes may be distinguished by magnetic measurements. Since the outer
orbital complexes use high energy levels, they tend to be more reactive. The inner orbitals are sometimes
called inert orbitals.
(c) Distribution of d-electrons in
2g
t and
g
e sets in strong(er) and weak (er) octahedral ligand fields.
Ions Strong (er) field (low spin or spin paired Weak (er) field (high -spin or spin free
Complexes) (A AA AA
0
> P) complexes ) (A AA AA
0
<P)
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[197]
p q
2g g
t e n s
p q
2g g
t e n s
Configuration Configuration
d
1
1 0
2g g
t e 1 1/2
1 0
2g g
t e 1 1/2
d
2
2 0
2g g
t e 2 1
2 0
2g g
t e 2 1
d
3
3 0
2g g
t e 3 3/2
3 0
2g g
t e 3 3/2
d
4
4 0
2g g
t e 2 1
3 1
2g g
t e 4 2
d
5
5 0
2g g
t e 1 1/2
3 2
2g g
t e 5 5/2
d
6
6 0
2g g
t e
0 0
4 2
2g g
t e 4 2
d
7
6 1
2g g
t e 1 1/2
5 2
2g g
t e 3 3/2
d
8
6 2
2g g
t e 2 1
6 2
2g g
t e 2 1
d
9
6 3
2g g
t e 1 1/2
6 3
2g g
t e 1 1/2
d
10
6 4
2g g
t e 0 0
6 4
2g g
t e 0 0
Factors affecting the magnitude of
O
A
i) Oxidation state of the metal ion: The magnitude of
O
A increases with increasing ionic charge on the
central metal ion. As the ionic charge on the metal ion increases greater is the attraction for the ligands,
greater the repulsion and hence greater the magnitude of
O
A . ( ) ( )
3 4
6 6
Fe CN Fe CN
- -
    >
   
ii) Nature of the ligands: Based on experimental observation for a wide variety of complexes, it is possible
to list ligands in order of increasing field strength in a spectrochemical series. Although it is not possible
to form a complete series of all ligands with a single metal ion, it is possible to construct one from
overlapping sequences, each constituting a portion of the series:
2 3 2
F H O Cl NH en NO CN CO
- - - -
< < < < < < < (Increasing order of
O
A ).
NH
3
produces a greater splitting than H
2
O.
3
, , NH CN CO
-
, en are strong field ligands.
2
, F H O
-
are weak field ligands.

(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
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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 µ · - · ·
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[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.
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[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.

STABILITY OF COORDINATION COMPOUNDS
For a given metal and ligand the stability is generally greater, the greater the charge on the metal ion. Thus,
stability of coordination entitites of ions of charge 3+ is greater than the entities of 2+ ions.
( ) ( )
3 4
6 6
Fe CN Fe CN
- -
    >
   
Further. for the divalent ions of the first row transition elements, irrespective
of the ligand involved, the stabilities vary in the Irving -Williams order:
II II II II II II
Mn Fe Co Ni Cu Zn < < < < >
.
( ) ( ) ( )
3 2
2 2 2
6 6 6
; A H O Mg H O Na H O
- - -
      > >
     
The metal ions, ‘Class A acceptors like metals of groups 1 and 2, the inner transition elements and the early
members of the transition series (groups 3 to 6 like
4 6 7
, , Zr Cr Mn
- - -
) form their most stable coordination
entities with ligands containing N, O or F donor atoms.
The metal ions, class B acceptors like the transition elements - Rh, Pd, Ag, Ir Au and Hg having relatively full
d orbitals form their most stable complexes with ligands whose donor atoms are the heavier members as P,
S, I groups.
[ ] [ ]
3 3
6 6
FeF FeI
- -
> ;
[ ] [ ]
2 2
4 4
HgI HgF
- -
>
The stability also depends on the formation of chelate rings. If L is an unidentate ligand and L-L, a didentate
ligand and if the donor atoms of L and L-L are the same element, then L-L will replace L. The stabilisation due
to chelation is called the chelate effect. ( ) ( )
3 3
3
3 6
Co en Co NH
- -
    >
   
. It is of great importance in biological
systems and analytical chemistry. The chelate effect is maximum for the 5- and 6- memebered rings. In
general, rings provide greater stability to the complex.
If a multidentate ligand happens to be cyclic, a further increase in stability occurs. This is termed the macrocyclic
effect.

ORGANOMETALLIC COMPOUNDS AND THEIR APPLICATIONS
A) These compounds may be classified into three classes
i) Sigma ( ) o bonded complexes
In these complexes , the metal atoms and carbon atom of the ligand are bonded with a sigma bond in which
ligand contributes one electron and is therefore called one electron donor
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[201]
EXAMPLES
a) Grignard Reagent R –Mg –X where R is a alkyl or aryl group and X is halogen
b) ( ) ( ) ( ) ( )
3 3 2 5 2 3 2 2 5
4 4 6 6
CH Li, CH Sn, C H Pb,Al CH ,Al C H - etc
C H
3
Al
C H
3
CH
3
CH
3
Al
CH
3
CH
3
Bridging groups
ii) pie (r) bonded organometallic compounds
These are the compounds of metal with alkenes, alkynes, benzene and other ring compounds.
e.g. Zeise’s salt ( )
2
3 2 4
K PtCl C H
 
q -
 
Cl
Cl
Pt
Cl
H
C
H
C
H
H
K
+
Potassium trichloro (
2
q - ethylene) platinate(II)
The coordinated alkene will have a longer C - C bond than in pure alkene. This is due to the pumping
of metal d electrons into
* r
orbitals of the alkene.
Ferrocene ( )
5
5 5
2
Fe C H q -
-1
-1
Fe
+
2
bis(
5
q - cyclopentadienyl) iron(II), it is a Sandwich complex and diamagnetic.
Dibenzenechromium ( )
6
6 6
2
Cr C H q -
Cr
bis(
6
q - benzene) chromium (O)
iii) & o r bonded organometallic comp. eg Metal carbonyls ; ( ) ( )
4
6
, Ni CO Cr O
b) Some of the applications of organometallic compounds are as follows
1) Tetraethyllead is used as antiknock compound in gasoline
2) Wilkinson’s catalyst [Rh(PPh
3
)
3
Cl] is used as homogeneous catalyst in the hydrogenation of alkenes.
3) The extraction and purification of nickel is based on the formation of organometallic compound
4) The formation of Ni(CO)
4
at 50-80
0
C and its decomposition at 150-180
0
C is used in the extraction of
nickle by MONDS PROCESS
Zeigler Natta catalyst (trialkyl aluminium + titanium tetrachloride) acts as a heterogeneous catalyst in
the polymerisation of ethylene to polyethylene.
5) ( )
2
8
Co CO Catalysis: Hydroformylation reaction
2 2 2 3 2
CH CH H CO CH CH CHO · - - ÷
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[202]
6) Wackers oxo process ( )
2 2
PdCl CuCl -
2 2 2 3
CH CH H O CH CHO · - ÷
Application of coordination compounds:
1). Qualitative Analysis:
(a) AgCl is soluble in aq.
3
NH due to complex formation ( )
3
2
Ag NH Cl  
 
.
(b) ( )
3
2
. 2
DMG
aq NH
Ni Ni DMG
-
÷÷÷÷
Scarlet or Rosy red ppt.
(c)
( )
2
3
2
5
4
. dil HCl
Fe Fe H O NCS
NH SCN
-
-
 
 
Blood red color
(d)
( )
2
2 4
4
NH SCN
Co Co NCS
acetone
Blue color
-
-
 
 
(e) Sodium nitro prusside: ( ) ( )
2
5
Na Fe CN NO  
 
. Note that NO is +1 state. Oxidation state of Fe is
2 5 1 0, 2 x x - - - - · · - . This is used to test the sulphide ion in alkaline medium (Lassighnes test)
( ) ( ) ( ) ( )
2 2
2
5 5
Fe CN NO S Fe CN NO S
Violet colour
- -
-
    - ÷
   
2). Quantitative Analysis:
(a) Complexometric titrations using
2
Na EDTA(EDTA). Many metal ions form complexes with EDTA.
By this titration, one can estimate
2 2 2 2 2 2
, , , , , Zn Cd Co Ni Ca Mg
- - - - - -
etc.
(b) Molarity is used rather normality
Eg: 1000 cc - 1MEDTA solution
=
63.54 g of
2
Zn
-
.
(c) Hardness of water is determined by EDTA method.
2
Ca
-
and
2
Mg
-
are estimated together in water
by EDTA titration. Hhardness of water is expressed as mg of
3
CaCO in 1 lit. of water. (PPm)
For the calculations use
1000 cc - 1 MEDTA solution
=
100 g of
3
CaCO .
3) Biological systems:
(a) Haemoglobin: Heme + globin (globular protein).
Heme :
2
Fe
-
-
Porphyrin ring (made up of 4 pyrrole rings, macrocyclic ligand).
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[203]
deoxy Hb,
( )( )
4 2
2 g g
t e oxy Hb
( )( )
6 0
2 g g
t e
High spin complex Low spin complex
Everytime in our body the transition from ! HS LS occurs ÷÷÷
3
, , CO CN pph
-
are poisonous as they bind to iron atom irreversibly.
(b) Carboxy peptidase carbonic anhydrase: Zn containing enzyme.
(c) Vitamin
12
B : Cyano cobalamine
2
Co
-
-
corrin ring .
A naturally occuring compound with Co - C bond!
(d) Nitrogenase : Atmospheric fixation of
2
N by Azotobacterium or Rhizobium. Nitrogenase can reduce
2
N to
3
NH . It has Fe - Mo - S cluster complex.
(e) Superoxide dismutase: Cu - Zn enzyme
(f) Cisplatin : ( )
3 2
2
Cis Pt NH Cl   -
 
anti cancer drug.
(g) Chlorophyll:
2
Mg
-
+ Porphyrin ring + Phytin photosynthesis. ( )
2 2 6 11 5 2
n
CO H O C H O O - ÷ -
KEY CONCEPTS
 Transition elements have parlty filled d-orbital.
 The covalent radii of transition elements decrease from left to right across a row, until near the end when
size increaes slightly.
 All the transition elements are metals and good conductors of heat and electricity, have a metallic luster
and are hard strong & ductile.
 Low atomic volume and high denisty.
 Melting and boiling points of transition elements are generally very high.
 The first ionization energy gradually increases from left to right. Generally, the ionization energies of
transition elements are intermediate between those of S & P-block elements.
 Transition elements usually exist in several different oxidation states and the oxidation states change in
units of one.
 Compounds of transition element and inner transition elements are colour due to presence of incomplete
d-or f-sushells.
 When solutions containing two or more simple stable salt s in stoichiometric proportions are allowed to
evaporate, addition compounds are formed
 Addition compounds which lose their identify in solution are called double salts.
 The neutal molecules or ions which are linked directly with the central metal atom ion are called ligands.
 The total number of atoms of ligands that can coordinate to the central metal atom/ion is called coordination
number
 The central metal and ligands are enclosed in a square bracket called coordination sphere
 The total number of electrons, which the central metal atom appears to possess in the complex,
including those gained by it in bonding is called effective atomic number (EAN)
 Primary valency corresponds to the oxidation state of the metal ion.
 Secondary or auxiliary valency is also termed as coordination number of the central metal . It is non-
ionic or non-ionisable, but directional.
 Sidgwick theory explains the stability of metal carbonyls using EAN rule.
 Paulings valence bond theory uses the hybridization to explain the geometry and the magnetic nature
of the complexes.
 Ligand field theory explains the splitting of d orbitals in octahedral, tetrahedral and square planar
complexes.
 Direct M - C or o r bond should present in an organometallic compound.