CHEMISTRY
CHAPTER - 9
COORDINATION COMPOUNDS
A COORDINTION COMPOUND CONTAINS A CENTRAL METAL ATOM LINKED TO A
NUMBER OF OPPOSITELY CHARGED OR NEUTRAL MOLECULES CALLED LIGAND.
NOMENCLATURE RULES FOR COMPLEXES
1) Order of naming ions
The cation, whether simple or complex, is named first followed by the
anion. The name of complex part written as one word.
K4[Fe(CN)6] Potassium hexacyanoferrate(II)
2) Naming of the coordination entity
The ligands are named first followed by the name of central metal.
[Pt(NH3)2Cl2] Diamminedichloridoplatinum(II)
3) Naming of ligands
Negative ligands- end in -O
Cl- chlorido Br- bromido
CN- cyano OH- hydroxo
NO2- nitrito-N ONO- nitrito-O
C2O42- oxalato SCN- thicyanato
NCS- isothiocyanato SO42- sulphato
Neutral ligands – no special ending
NH2-CH2-CH2-NH2 Ethane-1,2-diamine or (ethylenediamine)
NH3 ammine
H2O aqua
CO carbonyl
NO nitrosyl
4) Prefixes to indicate the number of ligands
More then one ligand, bi, tri, tetra, penta, hexa etc..
If it is a polydentate ligand, bis, tris, tetrakis, pentakis etc..
(The name of ligand in such cases is placed in brackets without any hyphen)
5) Order of naming
Ligands in a coordination entity are named in alphabetical order.
[Pt(NH3)4Cl(NO2)]SO4 tetraamminechloridonitrito-N-platinum(IV)sulphate
6) Oxidation state of central metal atom
Indicated by Roman numeral In brackets at the end of the coordination
entity.
Nomenclature of complexes
1. [Co(NH3)5Cl]Cl2
2. [Cr(H2O)4Cl2]Cl
3. [Cr(H2O)6]Cl3
4. [Pt(NH3)6]Cl4
5. [Co(NH3)3(NO2)3]
6. [Pt(NH3)2Cl2]
7. [Ag(NH3)2]Cl
8. [Co(NH3)4SO4]NO3
9. [Co(NH3)4(H2O)Br](NO3)2
10. K3[Fe(CN)6]
11. K3[Fe(C2O4)3]
12. [Ni(CO)4]
13. [CoCl2(en)2]SO4
14. [Cr(en)3]3+
The formula of the complex Diamminechloro(ethylenediamine) nitroplatinum (IV) chloride is
(a) [Pt (NH3)2Cl(en)NO2]Cl2 (b) Pt[Pt(NH3)2(en)Cl2NO2]
(c) Pt(NH3)2(en)NO2]Cl2 (d) Pt(NH3)2(en) NO2Cl2]
ISOMERISM IN COORDINATION COMPLEXES
A) Structural isomerism
Same molecular formulae and difference in structural arrangements.
1) IONISATION ISOMERISM
This type of isomerism is due to the interchange of groups between the
coordination sphere and ions outside this sphere.
[Co(NH3)5Br]SO4 [Co(NH3)5(SO4)]Br
Give white ppt BaSO4 with BaCl2 Give a pale yellow ppt with AgBr
with AgNO3
2) Hydrate isomerism(solvate isomerism)
It is due to the difference in the number of water molecules present as
ligands (i.e, in the coordination entity) and as molecules of hydration (i.e,
outside the coordination entity).
• [Cr(H2O)6]Cl3 violet
• [Cr(H2O)5Cl]Cl2.H2O gray green
• [Cr(H2O)4Cl2]Cl.2H2O Dark green
3) Linkage isomerism
• This type of isomerism is shown by coordination compounds
containing monodentate ligands with more than one donor
atom(ambidentate ligands)
4) Coordination isomerism
• The isomerism arises due to interchange of ligands between two
coordination spheres.
• [Co(NH3)6] [Fe(CN)6]
• [Co(CN)6] [Fe(NH3)6]
B) STEREO ISOMERISM
• Isomerism which differ in the spatial arrangement of ligands around
in central metal atom are called stereoisomers.
Types
(1) Geometrical isomerism
(2) Optical isomerism
Geometrical isomerism or Cis -trans
isomerism
• When two identical ligands occupy adjacent positions
around the central metal atom, the isomer is called cis
and when they occupy opposite positions, the isomer
is called trans.
a) Square planar complexes(Mx2y2))
[Pt(NH3)2Cl2]
(b) Octahedral complexes(Ma4b2)
[Co(NH3)4Cl2]+
[CoCl2(en)2]+
• Another type of geometrical isomerism occur in octahedral
coordination compounds of type Ma3b3.
• If identical ligands occupy adjacent positions at the corners of the
octahedral face, the isomer is called facial (fac) isomer.
• When the positions of similar ligands are around the meridian of the
octahedron, the isomer is known as meridian (mer) isomer.
Optical isomerism
• It differ in their action towards polarized light.
• The isomer which rotates the plane of polarization of light to the right
is called dextro rotatory (d or +)
• Towards left laevo (l or -)
Condition
complex which contain two or three identical bidentate ligands.
[Co(en)3]3+
tris(ethylenediamine)cobalt (III)
• Similarly the complex [CoCl2(en)2]+ shows optical isomerism. This
complex also shows geometrical isomerism. It exists in cis and trans
forms. Of these, the cis form is optically active and exist in d and l
form.
[CoCl2(en)2]+
Werner’s theory
1. In coordination compounds, metal atom exhibit two types of valencies, primary or ionisable valency and
secondary or non-ionisable valency.
Primary valency - Oxidation state
Secondary valency - coordination number
2. Primary valency only satisfied by anions while secondary by anions or by neutral molecules.
3. Every metal atom has a fixed number of secondary valencies.(i.e, it has a fixed coordination number)
4. The secondary valencies are always directed towards fixed positions in space. This gives rise to definite
geometrical shape for coordination compounds and makes stereoisomerism possible.
VALANCE BOND THEORY( VBT)
1) The central metal atom in the coordination compound provides a
[Link]. empty orbitals for the formation of coordinate bonds with
suitable ligands. The no of empty orbitals thus made available i.e equal
to the coordination no of the metal atom.
2) The appropriate empty atomic orbitals of the metals hybridise to
form a set of equivalent orbitals with definite geometry.
COORDINATION NUMBER HYBRIDISATION GEOMETRY
4 sp3 tetrahedral
4 dsp2 Square planar
6 Sp3d2 or d2sp3 octahedral
3) In each ligand at least one orbital containing a lone pair of electron (i,e,
filled orbital).
4) The empty hybridized orbitals of the central metal atom overlap with the
filled orbitals of the ligands to form metal – ligand coordinate bonds.
Octahedral complexes Strong ligands
A) [Co(NH3)6]3+ Hexaammine cobalt (III) NH3, CN-,CO
B) [Fe(CN)6]3- Hexacyanoferrate (III) Weak ligands
F -, Cl-
C) [Fe(CN)6] 4- Hexacyanoferrate (II)
D) [CoF6]3- Hexafluorocobaltate (III)
Square planar complexes
A) [Ni(CN)4]2- Tetracyanonickelate (II)
Tetrahedral
A) Ni(CO)4 Tetracarbonylnickel (0)
B) [NiCl4]2- Tetrachloridonickelate (II)
1. [Co(NH3)6]3+
2. [Fe(CN)6]3-
3. [Fe(CN)6]4-
4. [CoF6]3-
5. [Ni(CN)4]2-
6. Ni(CO)4
7. [NiCl4]2-
Inner orbital complexes (low spin complexes)
• If the complex is formed by the use of inner (n-1)d orbitals for
hybridization (eg, d2sp3).
• In the formation of inner orbital complex, the electrons of the metal
ion are forced to pair up. So such a complex will have either no
unpaired electron or will have few unpaired electrons.
• Eg: [Fe(CN)6]3-
[Fe(CN)6]4-
Outer orbital complexes(High spin complexes)
• If the complex is formed by the use of outer nd orbitals for
hybridization (eg, sp3d2).
• The complex will generally have large number of unpaired electrons.
• Eg: [CoF6]3-
[Fe(H2O)6]3+
Limitations of VBT
1. It involve a number of assumptions.
2. It does not explain the colour exhibited by coordination
compounds.
3. In some cases, experimentally and theoretically calculated values of
magnetic moments are not the same.
4. It cannot give an exact explanation of thermodynamic or kinetic
stabilities of coordination compounds.
5. It does not clearly distinguish between weak and strong ligands.
CRYSTAL FIELD THEORY(CFT)
• CFT assumes the ligands to be point charges and the interaction between them
and central metal atom to be electrostatic in nature.
• All d-orbitals present in central metal atom have same energy (degenerate). But
this degeneracy is lost on approach of the ligands.
• This splitting of the degenerate d-orbitals of the metal ion into different sets of
orbitals having different energies under the influence of ligands is called ‘crystal
field splitting’.
Crystal field splitting in octahedral complexes
• In an octahedral complex, the coordination number of the metal is 6.
• As the ligand approach, the two d-orbitals lying along the axes (i.e,
dx2-y2 and dz2) get repelled more strongly and they get further raised
in energy. These orbitals are represented by eg orbitals.
• Other d-orbitals which orient in between the axes are lowered in
energy and these are represented by t2g orbitals.
• The energy difference between the two sets of orbitals (between eg
and t2g) is called crystal field splitting energy and is denoted by Δo.
0.0.6 Δo
0.0.4 Δo
Crystal field splitting in tetrahedral complexes
• In tetrahedral arrangement of four ligands, the three d-orbitals dxy,
dyz and dxz are pointing close to the direction in which ligands are
approaching.
• As a result of this, the energy of these orbitals increases more than
that of other two d-orbitals (dx2-y2 and dz2).
Factors which determine the magnitude of
orbital splitting energy (Δ)
(1) Oxidation state of metal ion
Higher the oxidation state – greater the value of Δ
(2) Geometry of the complex
The magnitude of orbital splitting for tetrahedral complexes (Δt) will be
less compared to that of octahedral complexes (Δ0)
(3) Nature of the ligand
❑Strong ligands such as CN-, NH3 etc. produces a strong field and cause
large splitting (Strong field ligands).
❑Weak ligands produces a weak field and cause small splitting (weak
field ligands).
Electronic arrangement of coordination
compounds according to CFT
SPECTROCHEMICAL SERIES
• The arrangement of ligands according to the magnitude of crystal
field splitting (Δ).
• In general, ligands lying above H2O are called strong ligands while H2O
and ligands lying below are considered as weak ligands.
Colour of coordination compounds
METAL CARBONYLS
• These are organometallic compounds in which carbon monoxide (CO) acts as ligands.
• The organometallic compounds which contain only carbonyl ligands are called homoleptic
carbonyls.
Eg: Fe(CO)5 Pentacarbonyliron(0)
Ni(CO)4 Tetracarbonylnickel(0)
❑The metal-carbon bond in these compounds have both σ and π character. The M-C σ bond is
formed by the overlap of orbital containing lone pair of CO with the vacant orbital of metal.
❑The M-C π-bond is formed by the overlap of filled d-orbital of metal with the vacant antibonding
π* orbital of CO.
Stability of coordination compounds
• The stability of coordination compounds in solution refers to the
degree of association between the metal ion and ligand involved in
the state of equilibrium.
• M + nL ↔ MLn
[𝑀𝐿𝑛]
•K= 𝑛 K= stability constant, 1/K = instability constant
𝑀 𝐿
• Higher the value of K, greater is its thermodynamic stability in
solution.
Factors affecting stability of a complex
1. Charge on the central ion (greater the charge-greater stability)
2. Basic nature of ligand (greater the basic strength-greater stability)
3. Presence of chelate ligands (greater stability)
Application of coordination compounds
(I) Qualitative analysis
• The presence of Fe3+ ions is confirmed by the formation of a deep blue
precipitate with potassium ferrocyanide solution.
4Fe3+ + 3K4[Fe(CN)6] Fe4[Fe(CN)6]3 + 12K+
Iron(III)hexacyanoferrate(II) – PRUSSIAN BLUE
• The presence of Ni2+ is confirmed by its reaction with dimethyl glyoxime.
ROSE RED PPT
(2) Quantitative analysis
• Hardness of water is due to the presence of Ca 2+ and Mg2+ ions. These
ions form stable complexes with EDTA. So hardness of water can be
determined by direct titration with EDTA.
(3) In biological system
Chlorophyll - Mg
Haemoglobin - Fe
Vit B12 (cyanocobalamine) - Co
(4) extraction of metal
Ag and Au are extracted from their ores through the formation of
cyanide complexes.
(5) In medicine
EDTA – lead poisoning
Treatment for cancer
(6) As catalyst
Wilkinson’s catalyst
RhCl(PPH3)3 - Hydrogenation of alkenes
