Isomerism in Coordination
Compounds
Isomers
Compounds with the same molecular
formula but different arrangement of
atoms in space
Major Types
1. Structural isomers
2. Stereoisomers
Isomerism
Structural Isomers
Compound with different atomic bond
connectivity.
Stereoisomers
Same atomic connectivity but different
arrangement.
Structural Isomers
Coordination-sphere isomers
◦ In this case compound is made up of cation and
anion and the isomerism arises due to interchange of
ligands between complex cation and complex anion
Example:
[Co(NH3)6][Cr(CN)6] vs [Cr(NH3)6][Co(CN)6]
hexaaminecobalt(III) hexacyanochromate(III)
hexaaminechromium(III) hexacyanocobaltate(III)
Ionization Isomers
Interchange of an ionic ligand with first coordination
sphere with an anion outside coordination sphere
Example: [Co(NH3)5Br]SO4
[Co(NH3)5SO4]Br
[PtCl2(NH3)4]Br2
[PtBr2(NH3)4]Cl2
Ionization Isomers
Example 1
[Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl
Consider ionization in water
[Co(NH3)5Cl]Br [Co(NH3)5Cl]+ + Br-
[Co(NH3)5Br]Cl [Co(NH3)5Br]+ + Cl-
Ionization Isomers
Example 2
[Co(NH3)5Cl]Br vs. [Co(NH3)5Br]Cl
Consider precipitation
[Co(NH3)5Cl]Br(aq) + AgNO3(aq) [Co(NH3)5Cl]NO3(aq) + AgBr(s)
[Co(NH3)5Br]Cl(aq) + AgNO3(aq) [Co(NH3)5Br]NO3(aq) + AgCl(aq)
Hydrate Isomers
Hydrate isomers have the same composition but differ
In the number of water molecules present as ligands
And the phenomenon is called hydrate isomerism.
Examples : [Cr(H2O)6]Cl3
[Cr(H2O)5Cl]Cl2.H2O
pentaaquachlorochromium (III) chloride monohydrate
[Cr(H2O)4Cl2]Cl.2H2O
tetraaquadichloro chromium (III) chloride dihydrate
Hydrate Isomers
i) six H2O in coordination sphere -Violet
ii) five H2O and one Cl in coordination sphere - Dark Green
iii) four H2O and two Cl in coordination sphere - Green
Linkage isomers
◦ difference in the atom of a ligand bonded to
the metal in the complex
Example
◦ [Co(NH3)5(ONO)]2+ vs. [Co(NH3)5(NO2)]2+
◦ [Co(NH3)5(SCN)]2+ vs. [Co(NH3)5(NCS)]2+
Co-SCN vs. Co-NCS
Linkage isomers
Nitro ligand as an N-donor
Nitrito ligand as an O-donor
Linkage isomers
2,2’’-bipyridine -bipyridine
Two compounds formed by the linkage isomer of bpy is
shown. Small changes in ligand bonding could result in
dramatic chemical property change
Stereoisomers
Geometric isomers
Square Planar:
Compound type No. of isomers
Ma2b2 (cis- and trans-)
Octahedral:
Compound type No. of isomers
Ma4b2 (cis- and trans-)
Ma3b3 (fac- and mer-)
MAA2b2 (cis- and trans-)
Geometrical isomer
◦ cis- isomers: have identical groups of atoms
(ligands) are adjacent to each other in structural
formula.
◦ trans- isomers: have identical groups of atoms
(ligands) opposite sides from each other in structural
formula.
◦ meridinal isomers (mer-): placing 3 identical ligands
in a plane bisecting the molecule of the octahedral
◦ facial isomers (fac-): placing 3 ligands on one
triangular face of the octahedral
FOUR-COORDINATE COMPLEX –
square planar
Geometric Isomers of Pt(NH3)2Cl2: In the cis
isomer, atoms are on the same side. In the trans
isomer, atoms are on opposite sides.
SIX-COORDINATE COMPLEX -
octahedral
Geometric Isomers of [Co(NH3)4Cl2]Cl:
SIX-COORDINATE COMPLEX -
octahedral
Complexes of formula ML3L’3 may have 2 isomeric
formed called fac- and mer- Cl
L and L’ :monodentate ligand
H3N
Cl Cl
Co
H3N
H3N Cl Cl
Co
H3N Cl Cl
NH3
NH3
N
fac-[Co(NH3)3Cl3] Cl
Co
N
Cl
N
N
N N
N
Co
N N N
N
Co
N N N
N N
fac-[Co(dien)2]3+
N
N
Co
N
N
N
SIX-COORDINATE COMPLEX -
octahedral
NH3 NH3
H3N Cl
Co H3N
Cl
Cl Cl Cl
Co
Cl
NH3
mer-[Co(NH3)3Cl3] NH3
N N
N N N
Co Co
N
N N N
N
N
N
mer-[Co(dien)2]3+
left is mer[Co(NH3)3(H2O)3]2+ right is fac[Co(NH3)3(H2O)3]2+
Geometric isomers
diaminebischloroplatinum(II)
Geometric isomers
Cis trans
Geometric isomers
cis isomer trans isomer
Pt(NH3)2Cl2
Geometric isomers
cis isomer trans isomer
[Co(H2O)4Cl2]+
Stereoisomers
Optical isomers
Isomer complex in which the atomic connection
are the same but arrangement is such that the
two complexes are not superimposable.
Optical isomer
Enantiomers have:
SAME : melting points, boiling points, dipole moments, solvent
capabilities
DIFFERENT : ability to rotate the plane of polarized light in
opposite directions
Polarimeter : to measure the rotation of polarized light by
optical isomers
Plane-polarized light is obtained by passing ordinary light
through a polarizing filter.
Example 1
Stereoisomers- optical isomers or enantiomers, are mirror
images of each other.
Just as a right hand will not fit into a left glove, two
enantiomers cannot be superimposed on each other.
A molecule or ion that exists as a pair of enantiomers
is said to be chiral.
Example 2
mirror plane
cis-[Co(en)2Cl2]+
Example 2 rotate mirror image 180°
180 °
Example 2
nonsuperimposable
cis-[Co(en)2Cl2]+
Example 2
enantiomers
cis-[Co(en)2Cl2]+
Example 3
mirror plane
trans-[Co(en)2Cl2]+
Example 3 rotate mirror image 180°
180 °
trans-[Co(en)2Cl2]+
Example 3
Superimposable-not enantiomers
trans-[Co(en)2Cl2]+
Properties of Optical Isomers
Enantiomers
◦possess many identical properties
(solubility, melting point, boiling
point, color, chemical reactivity)
A molecule or ion that exists as a pair of enantiomers
is said to be chiral.
Uses of Coordination Compounds
Dyes and Pigments: Coordination compounds have been used from the earliest
times as dyes and pigments, for example madder dye which is red, was used by
the ancient Greeks and others. It is a complex of Hydroxyanthraquinone. A more
modern example is the pigment copper phthalocyanine, which is blue.
Analytical Chemistry: You have already encountered many such uses during the
laboratory course.
(a) Colour Tests: Since many complexes are highly coloured they can be used as
colourimetric reagents e.g. formation of red 2,2'-bipyridyl and l,l0-phenanthroline
complexes as a test for Fe(II)
(b) Gravimetric Analysis: Here chelating ligands are often used to form insoluble
complexes e.g. Ni(DMG)2 and Al(oxine)3 (see laboratory manual).
(c) Complexometric Titrations and Masking Agents: An example of this is the use of
EDTA in the volumetric determination of a wide variety of metal ions in solution, e.g.
Zn2+, Pb2+, Ca2+,Co2+, Ni2+, Cu2+, etc. By careful adjustment of the pH and using
suitable indicators, mixtures of metals can be analysed, e.g. Bi3+ in the presence of
Pb2+ (see laboratory manual). Alternatively, EDTA may be used as a masking agent
to remove a metal ion which would interfere with the analysis of a second metal ion
present.
Sequestering Agents: Related to their use as masking agents is the use of
ligands for "sequestering" i.e. for the effective removal of objectionable ions from
solution in industrial processing, e.g. EDTA is used to "soften" water. The addition
of EDTA to water is used in boilers etc., to prevent "scaling" or build up of insoluble
calcium salts.
Extraction of Metals: Sometimes certain metals can be leached from their ores
by formation of stable complexes e.g. Ag and Au as complexes of cyanide ion.
Bio-Inorganic Chemistry: Naturally occurring complexes include haemoglobin,
chlorophyll, vitamin B12 etc.
EDTA and other complexing agents have been used to speed the elimination of
harmful radioactive and other toxic elements from the body. (e.g. Pb2+). In these
cases soluble metal chelate complexes are formed.
Chemo-therapy: an example here is the use of cis-PtCl2(NH3)2 as an anti-tumour
drug.
