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Complex ions
N Goalby
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Complex ion formation

A complex ion is formed when a metal ion is surrounded
by ligands which are bonded by co-ordinate bonding
into the metal ion
A ligand is a molecule or negative ion which can donate a
lone pair of electrons. eg H2O, NH3, amines, Cl-, CNThe number of ligands
bonded to the metal ion is
called the co-ordination
number.
The co-ordination number
exceeds its oxidation state.

2+

OH2
H2O
H2O

Co

OH2
OH2

OH2

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COMPLEX FORMATION

Lewis base
Lewis acid

electron pair donor (ligands are Lewis bases)

electron pair acceptor

Cl

In the formation of complex

ions the ligand is the Lewis
base as it donating a pair of
electrons in the dative
covalent bond and the
metal ion is the Lewis acid

2-

Cu
Cl

Cl
Cl

Ligands form co-ordinate

bonds via lone pairs

Shapes of Complex ions: Octehedral

Most common complex ions
have a coordination number 6
(i.e six ligands). The shape is
called octahedral.

2+

OH2
H2O
H2O

Ni

OH2
OH2

OH2

[Ni(H2O)6]2+
All the bond angles are 90
The octahedral complexes are
usually with small ligands such
as H2O and NH3

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Shapes of Complex ions: Coordination number 4

There are two shapes with a coordination number of 4
Cl

Tetrahedral complexes
are more common with
larger ligands e.g. Cl-

2-

Cu
Cl

Bond angle 109

Cl
Cl

Square planar
Bond angle 90

2-

H3 N

Cl

Pt

H3 N

Cl

Occur in Pt2+ complexes

Shapes of Complex ions: linear

Linear
coordination number 2
+
H 3N
Silver commonly forms linear
complexes e.g. [Ag(NH3)2]+,
[Ag(S2O3)2]3- and [Ag(CN)2]-).

Ag

NH3

diamminesilver(I)
Bond angle 180

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Four Common Structures Of Complex Ions

NH3
NH3
NH3

NH3

Ag+

Pt2+

NH3

NH3

Linear

Square planar
NH3

NH3
NH3

NH3
Co3+
Zn2+

NH3

NH3

NH3

NH3

NH3

NH3

Tetrahedral

Octahedral

Examples of complex ions

2+

NH3
H3 N
Ni

H3 N

NH3
NH3

NC
NC

NH3

CN
Fe
CN
CN

Hexaamminenickel(II)
Cl

Hexacyanoferrate(II)

2-

Cu
Cl

4-

CN

H 3N

Ag

NH3

Cl
Cl

tetraachlorocuprate(II)

diamminesilver(I)

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Ligands
Unidentate ligands
These are ligands that can form one dative covalent bond with
the metal ion. They will generally have one lone pair. eg H2O,
NH3, OH-, Cl-, CNBidentate ligands contain two donor atoms. They bond to the
metal ion through two atoms.

CH2 CH2 N

1,2-diaminoethane
NH2CH2CH2NH2

:
H

Ethanedioate(oxalate) ion

-OOC-COO-

Complexes containing bidentate ligands

3+

CH2
NH2

H 2C

NH2 CH
2

NH2
Cr

NH2

NH2
H2 C

CH2

CO2

O 2C
Cu

NH2
CH2

[Cr(NH2CH2CH2NH2)3]3+

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Multidentate Ligands
Hexadentate ligand
EDTA is a hexadentate ligand which has six
atoms that can form a dative covalent
bond.
It has a 4- charge (edta)4-

O
-O

O
CH2
N

-O

CH2

C O-

CH2

CH2 CH2 N

CH2

O-

EDTA
O

The EDTA4- anion has the formula

O
-O

-O

CH2
N

CH2

CH2

C O-

CH2

O
C

CH2 CH2 N
O-

CH2
CH2
N

CH2

Cu

with six donor sites(4O and 2N) and

forms a 1:1 complex with metal(II)
ions

O
N
C
O

As it can form six dative covalent bonds with

the metal ion, edta will only ever have a ratio of
one molecule of edta to one ion of the metal
eg [ Ni(edta)]2-

CH2

CH2
O

CH2
C
O

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Multidentate Ligands
Multidentate ligands form several co-ordinate bonds
haem

H2C
CH3
H3C
N

N
CH2

Fe
N
H3C

N
CH3

COOH

COOH

What types of bonding are present in the following

compound containing a complex ion?

K3[Fe(CN)6]
Ionic bonding between the potassium and the complex
ion [Fe(CN)6]3Dative covalent bonding between the CN- ligand and the
Fe3+ ion
Covalent bonding in the CN- ion

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Two Coordination Compounds of Co(III)

NH3
H3N
H3N

3 Cl

NH3

2+

H3N

NH3

Cr

NH3

3+

NH3

Cr

H3N

Cl

H3N

2 Cl

H3N

CoCl3.6NH3

CoCl3.5NH3

3 free Clper formula

2 free Clper formula

[Co(NH3)6]Cl3

[CoCl(NH3)5]Cl2

extra

Isomers of Cr(H2O)6Cl3
OH2
H2 O
Cr

H2 O

OH2

3+

2+

H2 O

OH2
3 Cl

OH2

OH2

Cr

Cl

2 Cl

OH2

H2O

H2 O

H2 O

Will react with Ag+ on 1:3 ratio

Will react with Ag+ on 1:2 ratio

The free Cl- ions will react with Ag+ to form AgCl (s)
OH2
H2 O
Cl

Cr

OH2

+
Cl
OH2

Cl
Cl
2H2O

H2 O

Will react with Ag+ on 1:1 ratio

H2 O

Cr

+
Cl
OH2

Cl
2H2O

H2 O

Will react with Ag+ on 1:1 ratio extra

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Isomerism In Complex Ions

Structural isomers differ in the ligands that are attached to
the central atom or in the donor atoms through which the
ligands are bonded.
Geometric isomers differ in the arrangement of the attached
ligands, forming either cis- (same side) or trans- (opposite
sides) compounds.
Optical isomers are isomers that differ in their ability to rotate
the plane of polarized light. Each of the two molecules or
ions of an optical isomer is called an enantiomer and each
enantiomer rotates the plane-polarized light in opposite
directions.

key

Geometric Isomerism In A
Square Planar Complex
2-

H3 N
H3 N

Pt

Cl
Cl

Cis-Diamminedichloroplatinum(II)
Cisplatin

2-

H3 N
Cl

Pt

Cl
NH3

trans-Diamminedichloroplatinum(II)
transplatin

key

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Geometric Isomerism In An
Octahedral Complex

NH3

Cl

NH3

NH3

Cr

Cl

NH3

Cr

Cl

NH3

NH3

Cl

NH3

NH3

Cis-[CoCl2(NH3)4]+

trans-[CoCl2(NH3)4]+

extra

Optical Isomers

mirror

CH2

CH2

NH2

H2 C
NH2

2+

NH2
NH2 CH2

Co

NH2

H2N
CH2

NH2
CH2

CH2

H2 C
CH2

NH2

2+

CH2
NH2

Co
NH2

NH2

H2N

CH2
CH2

extra

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