ISOMERISM

IN COORDINATION
COMPOUNDS
 Structural Isomerism
This isomerism arises due to difference in the structure of complex compounds.
This isomerism is of following types:
 Ionization isomerism
These isomers have the same molecular formulae and are produced when the

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ligand given in the coordination sphere and anions present outside the
coordination sphere are exchanged with each other.
E.g.:- [Co(NH3)5Br]SO4 and [Co(NH3)5(SO4)]Br
Ionization isomers show different properties. e.g.., [Co(NH3)5Br]SO4(I) and
[Co(NH3)5 (SO4)] Br(II) which are ionization isomers to each other and show
different properties as mentioned below:
i. (I) is red-violet while (II) is red.
ii. When these isomers are dissolved in water, they give different ions
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Hydrate Isomerism

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Coordination Isomerism
This type of isomerism is shown by those complex compound which are
composed of complex cation and complex anion. Coordination isomers are
obtained when some or all ligand of both the coordination spheres are
interchanged with each other. Thus both the complex compounds of each of the

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following pairs are coordination isomers to each other. In these pairs the central
metallic atom in the two coordination spheres may be the same or different.
i. [Cr3+(NH3)6]3+[Cr3+(CN)6]3- and [Cr3+(NH3)4(CN2)]+ [Cr3+(CN)4(NH3)2]-
ii. [Cu2+(NH3)4]2+[Pt2+Cl4]2- and [Cu2+Cl4]2-[Pt2+(NH3)4]2+

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Linkage Isomerism
Linkage isomers are shown by those coordination compounds which contain
ambidentate ligands, since these ligands can coordinate to the central metal atom
through any of the two different available donor atoms. The linking of
ambidentate ligand to the metal atom through two different donor atoms gives
two different compounds which are related with each as linkage isomers.

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Examples of Linkage isomers are:-
i. [Co3+(NH3)5NO2]2+(I) and [Co3+(NH3)5ONO]2+ (II) are linkage isomers. In (I)
NO2_ ligand is linked with Co3+ ion through its N-atom while in (II), NO2-
ligand is linked with Co3+ ion through its o-atom. (I) is called penta
amminenitro cobalt (III) ion while (II) is called penta amminenitrito cobalt (III)
ion. (I) is yellow while (II) is red.

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Coordination position Isomerism
This type of isomerism is shown by those complex compounds which contain bridging ligands and
arises when the non-bridging ligands are differently placed round the central metal atom.
OH 2+

(NH3)4CO3+ CO3+ (NH3)2Cl2

OH Tetra Amine Cobalt (III)

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NH2
Cl(NH3)4Co3+ CO3+ (NH3)3Cl
OH Chloro Tetra Amine Cobalt (III)

These compounds are coordination position isomers to each other, since NH3 molecules and Cl-
ions are differently placed around the Co3+ ions.
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Polymerization Isomerism
This type of isomerism is found in complex compounds whose formulae appear
to be polymers of some simple compound. All these compounds have the same
ratio of metal atoms and ligands in them.
For e.g.
[CO(NH3)3(NO2)3] and [CO(NH3)6] [CO(NO2)6] are polymerization isomers to

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each other and the second complex is a dimer of the first complex. The ratio of
the Co3+ : NH3 : NO2- is 1: 3 : 3

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STEREO ISOMERISM
Geometrical Isomerism
The complex compounds which have the same ligands in the coordination
sphere but the relative position of the ligands round the central metal atom is
different are called geometrical isomers and the phenomenon is called
geometrical isomerism.

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In a given complex compound the two ligands may occupy positions either
adjacent to each other or opposite to each other.

1.Complexes with (C.N. 2 and 3)

Geometrical isomerism is not found in complex compounds with coordination
number 2 and 3, since in these cases all the positions occupied by the ligands
round the central metal atom atom are adjacent to one another.
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2.Tetrahedral complexes (C.N.=4)
Geometrical isomerism cannot be shown by tetrahedral complexes, since all the four ligands in this
geometry have adjacent position (i.e., cis position) to one another and all the four angles are the
same (=109.5 ˚).

3. Square Planar Complexes (C.N.=4)

A square planar complexes having similar ligands at adjacent positions (90˚ apart) is called cis-
isomer while two similar ligands at opposite positions (180˚ apart) is called trans-isomer.

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4. Octahedral Complexes
In an octahedral complexes, they are said to be in cis position. On the other hand,
if two similar ligands are lying on a straight line which passes through the centre,
they are said to be in trans position.

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Geometric Isomerism-Octahedral Complexes
1.Octahedral Complexes of (Ma4bc) type- An important example of this is
[Co3+(NH3)4(H2O)Cl]2+ ion. This ion has cis and trans isomers.
2.Octahedral Complexes of (Ma2b2c2) type-An important example of this is
[Pt4+(NH3)2(py)2Cl2]2+ ion.This ion has 5 possible isomers, although only 3 have been isolated.

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3.Octahedral Complexes of [Mabcdef] type-The only complex of this type is
[Pt4+(py)(NH3)(NO2)(Cl)(Br)(I)].It has 15 possible isomers theoretically, but only 3 have been
isolated.
4.Octahedral Complexes of M(AA)3 type-No geometric isomerism shown.

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Optical(or d-l or Mirror Images) Isomerism
• Optical isomers are two compounds which contain the same number and kinds of atoms, and
bonds (i.e., the connectivity between atoms is the same), and different spatial arrangements of
the atoms, but which have non-superimposable mirror images.
• Each non-superimposable mirror image structure is called an enantiomer. Molecules or ions
that exist as optical isomers are called chiral.

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Important Terms related to Optical Isomerism-

1.Optical Activity and Optically Active Complexes- The property of a

complex of rotating the plane of polarised light is called its optical activity & the
complex possessing this property is said to be optically active.

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2.Different Forms of Optically Active Complexes- These complexes exist
in 3 forms namely: d-form(dextro-rotatory),l-form(levo-rotatory),Optically
Inactive.
3.Condition for a Molecule to Show Optical Isomerism-For a molecule to
show optical isomerism(to exist in d-and l-forms) it should be Asymmetric(no
plane of symmetry) and should be non-superimposable on its mirror image.

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Optical Isomerism-Tetrahedral Complexes (C.N.=4)
1.Tetrahedral Complexes of [Ma4],[Ma2b2] and [Ma3b] type- This type does not
show isomerism because all ligands around M are exactly equivalent.

2.Tetrahedral Complexes of [Mabcd] type- In this there are 4 different ligands around M

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and this complex produces a pair of enantiomorphs.

3.Tetrahedral Complexes of Be(II),B(III),Zn(II) type- These exist in symmetrical

bidentate ligands forms with these metals.Some egs. are bis(salicylaldehydato)boron(III) ion,
bis(benzoylacetonato)beryllium(II).

Optical Isomerism-Square Planar Complexes (C.N.=4)

They have an axis of symmetry and so are optically inactive.

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Optical Isomerism In 6-Coordinated Complexes-Octahedral
Complexes
1.Octahedral complexes of [Ma4b2] and [Ma5b] : These complexes do not show
optical isomerism.
2.Octahedral complexes of [Ma4b2] and [Ma3b3] : [Ma4b2] exist in cis- and trans-
isomers they both are optically inactive.

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[Ma3b3] exists in cis (facial) or trans (meridional) isomers, both of them are
optically inactive and hence does not show optical isomerism.
3.Octahedral complexes of [Ma4bc]: This complexes do not show optical
isomerism
4.Octahedral complexes of [ma2b2c2] : [Pt 4+ (NH3)(PY)2Cl2]2+ ion is an important
example of this type. The cis isomer exists in two optical isomers which are
mirror images to each other. The trans form of this complex is optically
inactive.
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5.[Mabcdef] type complexes: [Pt4+ (py)(NH3)(NO2)ClBrI]0 is the only example
of this type. This complex has 15 geometrical isomers and each isomer is optically
active, giving 30 active optical isomers.

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6. [M(AA)3] type complexes: Due to absence of a plane or center of symmetry,
the octahedral complexes of this type are resolvable into dextro and levo forms.
For e.g. : [Co3+(en)3]3+
7.[M(AA)2a2] type complexes :
[Co3+(en)2cl2]+ion shows geometrical isomerism
and exist as a cis and trans isomer.The cis isomer is optically active
(d and l isomers) but trans isomer is optically inactive.
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8. [M(AA)2ab] type complexes: [CO3+(en)2(NH3)CL]2- ion exists in cis and
trans forms. Due to absence of plane in cis isomer it is optically active and can
be resolved into d and l forms. The trans isomer is optically inactive.
9.[M(AA)a2b2] type complexes: [Co3+(en)(NH3)2CL2]+ exists in cis- and
trans- isomers. The cis isomer is optically active and gives optical d and l isomers

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but the trans isomer is optically inactive.
10. [M(AB)3] type complexes: octahedral complex of this type exists in cis
and trans isomers and both of them are optically active and hence each gives a
pair of optical isomers in d and l forms.

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Thank Edith Ziona- 121317061011
Fatima Zohra- 121317061012

You Jaweria Fatima Mohammed-

121317061014
Tasneem Hyderabadwala- 121317061033