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Bonding in co-ordination compounds (Werner's Coordination theory)
Werner was able to explain the bonding in complex.
Primary valency (Pv) : This is non- directional and ionizable. In fact it is the positive charge on the metal
ion.
Secondary valency (Sv) : This is directional and non- ionizable. It is equal to the number of ligand atoms
co-ordinated to the metal (co-ordination number). Example :








Geometry and magnetic nature of some complexes


Atom/ion/com
plex
(1)
Configuration
(2)
Oxidati
on
state of
metal
(3)
Type of
hybridizat
ion
(4)
Geomet
ry
shape
(5)
No. of
unpair
ed
electro
ns
(6)
Magnetic
nature
(7)
Ni
2+
(d
8
)

+2 2
Paramagn
etic
[NiCl
4
]
2


+2 sp
3

Tetrahe
dral
2
Paramagn
etic
[Ni(CN)
4
]
2+


+2 dsp
2

Square
planar
0
Diamagne
tic
Ni

0 2
Paramagn
etic
Ni(CO)
4


0 sp
3

Tetrahe
dral
0
Diamagne
tic
[Ni(NH
3
)
6
]
2+



+2
sp
3
d
2
(oute
r)
Octahed
ral
2
Paramagn
etic
Mn
2+
(d
5
)

+2 5
Paramagn
etic
[Mn(CN)
6]
4


+2
d
2
sp
3
(Inne
r)
Octahed
ral
1
Paramagn
etic
[MnCl
4
]
2


+2 sp
3

Tetrahe
dral
5
Paramagn
etic
Cu
2+
(d
9
)

+2 1
Paramagn
etic
[CuCl
4
]
2


+2 sp
3

Tetrahe
dral
1
Paramagn
etic
[Cu(NH
3
)
4
]
2+
+2 dsp
2
Square
planar
1 Paramagn
etic

(1) (2) (3) (4) (5) (6) (7)
Cr
3+
(d
3
)

+3 3
Paramagn
etic
[Cr(NH
3
)
6
]
3+


+3
d
2
sp
3

(Inner)
Octahed
ral
3
Paramagn
etic
[Cr(H
2
O)
6
]
3+



+3
sp
3
d
2

(Outer)
Octahed
ral
3
Paramagn
etic
CO
3+
(d
6
)

+3 4
Paramagn
etic
[CoF
6
]
3


+3
sp
3
d
2

(Outer)
Octahed
ral
4
Paramagn
etic
[Co(NH
3
)
6
]
3+


+3
d
2
sp
3

(Inner)
Octahed
ral
0
Diamagne
tic
CO
2+
(d
7
)

+2 3
Paramagn
etic
[Co(H
2
O)
6
]
2+



+2
sp
3
d
2

(Outer)
Octahed
ral
3
Paramagn
etic
Fe
2+
(d
6
)

+2 4
Paramagn
etic
[Fe(CN)
6
]
4


+2
d
2
sp
3

(Inner)
Octahed
ral
0
Diamagne
tic
[Fe(H
2
O)
6
]
2+



+2
sp
3
d
2

(Outer)
Octahed
ral
4
Paramagn
etic
[Fe(NH
3
)
6
]
2+
Same +2
sp
3
d
2

(Outer)
Octahed
ral
4
Paramagn
etic
Fe
3+
(d
5
)

+3
Octahed
ral
5
Paramagn
etic