Course CHB-401 (B.Sc.

SEM-IV)
Inorganic Chemistry
Dr. Kamlesh Kumar
Department of Chemistry, B.H.U.

CONTENTS
1. Double Salts
2. Coordination or Complex Compounds
3. Ligands
4. Denticity of Ligands and Classification
5. Werner’s Theory
6. Sidgwick’s EAN Concept
7. Valence Bond Theory
8. Nomenclature of Coordination Compounds
9. Isomerism
1. DOUBLE SALTS
These are combination of two simpler salts and dissociate into their constituent ions in the solution.
These exist only in the crystalline states.
Examples: KCl • MgCl2 • 6H2O (Carnallite)
FeSO4 • (NH4)2SO4 • 6H2O (Mohr’s Salt)
K2SO4 • Al2(SO4)3 • 24H2O (Potash Alum)
K2SO4 • Cr2(SO4)3 • 24H2O (Chrome Alum)

2. COORDINATION OR COMPLEX COMPONDS

These compounds do not lose their identity in the solution and also, do not give test of their
constituent ions. These are formed from the combination of central metal atom or ion and electron
donating groups (ligands).

3. LIGANDS (LEWIS BASES)

Molecules or ions which can donate electron pair or pairs to the central metal atom or ion in a
coordination compound.
Oxygen donor ligands: H2O, ROH, R2O
Nitrogen donor ligands: NH3, RNH2, R2NH, R3N, pyridine
Halide anions: F-, Cl-, Br-, I-
-donor and -acceptors: CO, CN-, Phosphines (PR3), NO
-electron donor ligands: Organic molecules which do not have lone pair but have -electrons-
alkenes, alkynes, benzene
4. DENTICITY OF LIGANDS
This represents number of sites in a ligand by which it can bind with metal ion in a coordination
compound.
Classification of Ligands based on denticity
Monodentate ligand - one binding site
H2O, NH3, Cl-, CO etc.
Bidentate ligand – two binding sites

Tridentate ligand – three binding sites

Tetradentate ligand – Four binding sites

Pentadentate ligand – Five binding sites

hexadentate ligand – Six binding sites

5. WERNER THEORY (1893)
The most successful attempt to explain the formation of coordination compounds was made by
Alfred Werner in 1893. (Alfred Werner was first inorganic chemist to get Nobel Prize in 1913).
The basic postulates of Werner’s theory can be summarized as follows:
1. In coordination compounds, there are two types of valencies
(a) Primary or Principal valency : Ionizable and non-directional
(b) Secondary or Auxiliary valency : Nonionizable and directional
2. Primary valencies are satisfied by negative ions but secondary valencies are satisfied by
either negative ions or neutral molecules.
3. The number of secondary valency is fixed for a metal.
4. The secondary valencies are oriented in the fixed positions in the space. This is related to
the geometry of the coordination compound.
In complex ML6 with coordination number 6 (coordination number is another name of
secondary valency), there are three possible arrangements of ligand (L) around metal (M)
namely a planar hexagon, a trigonal prism and an octahedron (Fig. 1)

Fig.1: Possible arrangements of L around M in ML6

Werner find out how many isomeric forms of a complex can be prepared in the laboratory and he compared
this with the theoretical number for each of the possible shape or geometry (Table 1).
Table 1: Number of isomers predicted and experimentally found
Complex Planar hexagon Trigonal prism Octahedron Experimental
ML6 1 1 1 1
ML5L’ 1 1 1 1
ML4L’2 3 3 2 2
ML3L’3 3 3 2 2

These results strongly suggested the shape or geometry of ML6 is octahedral. However, this was
not absolute proof of shape since correct experimental condition for preparing all isomers may not
have been found.
Interpretation of Werner’s Theory with Example
Werner synthesized a series of compounds with varied CoCl3:NH3 ratio and deduced the structures
on the basis of experimental observations.

We can write formulae and structures of these complexes as:

Verification of Werner’s Theory

Later experiments on molar conductivity measurement showed that structure proposed by Werner were
correct and were in agreement with following:
Complex Ionizable Cl- Total Charges Molar Conductance
(mol-1ohm-1cm2)
[Co(NH3)6]Cl3 3 6 ~432
[Co(NH3)5Cl]Cl2 2 4 ~262
[Co(NH3)4Cl2]Cl 1 2 ~100
[Co(NH3)3Cl3] 0 0 0
The molar conductivity of cobalt complexes are comparable with known simple ionic compounds:
Complex Total Charges Molar Conductance
(mol-1ohm-1cm2)
NaCl Na+ Cl- 2 ~120
BaCl2 Ba2+ 2Cl- 4 ~260
3+ -
LaCl3 La 3Cl 6 ~393.5

Similarly, Werner was able to predict the shapes/geometries of [PtII(NH3)2Cl2] and [PdII(NH3)2Cl2]
as square planar because he isolated two different isomers.

LIMITATIONS
1. Werner’s theory is purely based on experimental observations. He did not give any theoretical
basis of secondary valency.
2. The geometries of complexes were predicted on the basis of number of isolated isomers.
However, it is not essential that all isomers could be prepared and isolated.
3. Secondary valency is also satisfy by positive ions e.g. NO+
4. It does not explain color, magnetic and thermodynamic properties of the coordination
compounds.
6. SIDGWICK’S EFFECTIVE ATOMIC NUMBER (EAN) CONCEPT
At the time of development of Werner’s theory, the theory of electronic structure of metal was
unknown. To explain the Werner theory in electronic concept, Sidgwick introduced the idea of a
coordinate bond. According to him, secondary valency proposed by Werner is special form of
covalent bond in which bonding electrons are furnished by a donor and accepted by an acceptor.
Once bond is formed it is not different from the covalent bond. For example in [Co(NH3)6]3+ , Co3+
accepts 12 electrons from six NH3 molecules.
Sidgwick also introduced the concept of effective atomic number (EAN). According to EAN rule,
when forming a complex, ligands are added until the total number of electrons on the metal ion
plus electrons donated by ligands becomes the same as the number of electrons in the next inert
gas.
EAN = [Atomic number - electrons lost in cation formation + electrons gained by coordination]
OR
EAN = [Atomic number + electrons gained in anion formation + electrons gained by coordination]
Examples
KMnO4 EAN of Mn = 25-7+8 = 26
K4[Fe(CN)6] EAN of Fe = 26-2+12 = 36
K3[Fe(CN)6] EAN of Fe = 26-3+12 = 35
[Ni(CO)4] EAN of Ni = 28-0+8 = 36
[V(CO)6]- EAN of V = 23+1+12 = 36
[V(CO)5]3- EAN of V = 23+3+10 = 36

LIMITATIONS
1. Although this rule is invariably obeyed by metal carbonyl complexes (exception V(CO)6) and
a number of complexes, there are large number of exceptions.
2. This rule unable to explain geometrical shapes of complexes.
3. This does not help to interpret the magnetic, spectral and thermodynamic behavior of
complexes
4. According to this rule many electron pairs are accepted by metal ion which would result
accumulation of negative charge on the metal. This is a serious problem and is against the
electropositive nature of the metals.
7. VALENCE BOND THEORY (VBT)
Pauling in 1931 was able to predict the geometries of many metal complexes on the assumption
that hybrid orbitals are involved in the formation of coordination complexes. The main features of
VBT are:
1. Each ligand is assumed to donate a pair of electron to the metal ion to form a coordinate
covalent M–L bond.
2. The central metal ion makes available a number of hybrid orbitals (equal to coordination
number) for the formation of M–L bond.
3. A –bond arises from the overlap of a vacant metal hybrid orbital and a filled orbital of
ligand.
4. In addition to –bond, there is possibility of –bond formation by overlap of filled d-orbital
of metal with vacant orbital of ligand.

Coordination Geometry Hybridization Examples

Number
2 Linear sp(spz) [Ag(NH3)2]+
3 Trigonal planar sp2(spxpy) [Ag(PR3)3]
4 Tetrahedral sp3(spxpypz) [Ni(CO)4]
3
sd (sdxydyzdxz) [MnO4]-
Square Planar dsp2(dx2-y2spxpy) [Ni(CN)4]2-
5 Trigonal bipyramidal sp3d(spxpypzdz2) [CuCl5]3-
Square pyramidal sp3d(spxpypzdx2-y2) [VO(acac)2]
6 Octahedral (outer sp3d2(spxpypzdx2-y2dz2) [Cu(H2O)6]2+
orbital complex)
Octahedral (inner d2sp3(dx2-y2dz2spxpypz) [Fe(CN)6]4-
orbital complex)
Let’s consider few examples to explain their geometries:
[Ag(NH3)2]+
Ground state electronic configuration of 47Ag is [Kr]4d105s1
4d 5s 5p
[Kr]

Since, Ag is in 1+ oxidation sate in the complex, ground state electronic configuration of Ag+ is
4d 5s 5p
[Kr]

Two electron pairs from two NH3 molecules will be accommodated in the sp hybrid orbitals as
shown below:
4d 5s 5p
[Kr]
sp hybrid orbitals

Accordingly, geometry will be linear.

[Ni(CN)4]4-
Ground state electronic configuration of 28Ni is [Ar]3d84s2

3d 4s 4p
[Ar]

Since, Ni is in zero oxidation sate in the complex ion, the above electronic configuration will be
same for complex also. CN- is ligand in the complex and it has tendency to pair the unpaired of
electrons in the metal ion. Accordingly, excited state electronic configuration will be

3d 4s 4p
[Ar]

Four electron pairs from 4 CN- ligands will be accommodated in the sp3 hybrid orbitals as shown
below:
3d 4s 4p
[Ar]
sp3 hybrid orbitals
Accordingly, geometry will be tetrahedral. Complex is diamagnetic because does not contain
unpaired electron.

(Note: In general carbon and nitrogen donor ligands have tendency to pair the unpaired electrons
but oxygen and halogen donor ligands do not)

[Fe(CN)6]4-
Ground state electronic configuration of 26Fe is [Ar]3d64s2

3d 4s 4p
[Ar]

Since, Fe is in 2+ oxidation sate in the complex ion and CN- is ligand, excited state electronic
configuration will be

3d 4s 4p
[Ar]

Six electron pairs from 6 CN- ligands will be accommodated in the d2sp3 hybrid orbitals as shown
below:
3d 4s 4p
[Ar]
d2sp3 hybrid orbitals

Accordingly, geometry will be octahedral (inner orbital complex because inner shell d-orbitals
involved in the bonding). Complex is diamagnetic because does not contain unpaired electron.
[Fe(CN)6]3-
Ground state electronic configuration of 26Fe is [Ar]3d64s2

3d 4s 4p
[Ar]

Since, Fe is in 3+ oxidation sate in the complex ion and CN- is ligand, excited state electronic
configuration will be

3d 4s 4p
[Ar]

Six electron pairs from 6 CN- ligands will be accommodated in the d2sp3 hybrid orbitals as shown
below:
3d 4s 4p
[Ar]
d2sp3 hybrid orbitals

Accordingly, geometry will be octahedral. Complex is paramagnetic because it contains one

unpaired electron.

[FeF6]3-
Ground state electronic configuration of 26Fe is [Ar]3d64s2

3d 4s 4p
[Ar]

Since, Fe is in 3+ oxidation sate in the complex ion and F- is ligand, excited state electronic
configuration will be

3d 4s 4p
[Ar]
Six electron pairs from 6 F- ligands will be accommodated in the sp3d2 hybrid orbitals as shown
below:

3d 4s 4p 4d
[Ar]
sp3d2 hybrid orbitals

Accordingly, geometry will be octahedral (outer orbital complex because outer shell d-orbitals
involved in the bonding). Complex is paramagnetic because it contains five unpaired electron.

Ni2+ ion can adopt any of the following configurations:

3d 4s 4p 4d
[Ar]
sp3 hybrid orbitals – Tetrahedral e.g. [NiCl4]2-

3d 4s 4p 4d
[Ar]
dsp2 hybrid orbitals – square planar e.g. [Ni(CN)4]2-

3d 4s 4p 4d
[Ar]
sp3d2 hybrid orbitals – Octahedral e.g. [Ni(NH3)6]2+

V.B. Theory failed to explain the geometry of [Cu(NH3)4]2+. Ground state electronic configuration
of 29Cu is [Ar]3d104s1

3d 4s 4p
[Ar]

Cu is in 2+ oxidation sate in the complex ion, the excited state electronic configuration will be

3d 4s 4p
[Ar]
The observed geometry for this complex is square planar and hence hybridization would be dsp2.
This was explained by promotion of one unpaired electron from 3d orbital to higher energy 4p
orbital leaving one 3d orbital vacant which is participated in the hybridization. Four electron pairs
from 4 NH3 ligands will be then accommodated in the dsp2 hybrid orbitals as shown below:

3d 4s 4p
[Ar]
dsp2 hybrid orbitals

Accordingly, geometry will be square planar. Complex is paramagnetic because it contains one
unpaired of electron.

LIMITATIONS
1. It cannot predict whether a coordination compound will be tetrahedral or square planar e.g.
[Cu(NH3)4]2+ is a planar complex but V.B. theory failed here to interpret the structure.
2. It is also failed to predict whether a complex is inner orbital complex or outer orbital complex.
3. It does not predict any distortion in symmetrical complexes (John-Teller distortions).
4. It does not attempt to explain the color of the complexes.
5. It cannot explain the temperature dependent paramagnetism of the complexes.
8. NOMENCLATURE OF COORDINATION COMPOUNDS
The basic rules of nomenclature are:
1. Name the cation first and then anion with space.
2. Naming of complex portion
(a) Number of Ligands: use di, tri, tetra, penta, hexa OR if necessary then bis, tris, tetrakis etc.
(b) Naming of Ligands:
 In alphabetical order, regardless of their charges.
 Anions end in ‘o’. This replaces the final 'e' when the anion ends with '-ide', '-ate' or '-ite'
as ‘–ido’, ‘-ato’, or ‘-ito’ (2005 IUPAC recommendations). Formerly, '-ide' was changed
to '-o' (e.g. chloride as chloro and cyanide as cyano etc)

F- Flourido CH3COO- Acetato O2– Superoxido

Cl- Chlorido H- Hydrido SCN- Thiocyanato-S
Br- Bromido OH- Hydroxido NCS- Thiocyanato-N
I- Iodido O2- Oxido NO2- Nitrito-O
CN- Cyanido O22- Peroxido NO2- Nitrito-N

 Neutral ligands as such except

NH3 ammine CO carbonyl
H2O aqua NO nitrosyl

 NO+ nitrosylium
(c) If complex is anionic, Latin name of metal will end with ‘ate’. Otherwise metal will named as
such if complex is cation or neutral.
Metal Latin name Metal Latin name
changed to changed to
Fe ferrate Cr chromate
Cu cuprate Ni nickelate
Ag argentate Co cobaltate
Au aurate Al Aluminate
(d) Oxidation state of metal will be written in Roman numeral in small bracket: (0), (I), (II), (III)
etc
(e) Bridging complex: Bridging ligands are separated by ‘–μ–’ for one bridging ligand or ‘di-μ–’
for two bridging ligands or ‘tri–μ–’ for three bridging ligands.
(f) For optical isomers use  or  and geometrical isomers cis- or trans- and fac- (facial) or mer-
(meridional)
Examples
K4[Fe(CN)6] potassium hexacyanidoferrate(II)
[CoCl(NH3)5]SO4 pentaamminechloridocobalt(III) sulfate
2+
[Cu(H2O)6] hexaaquacopper(II)
K2[CuBr4] potassium tetrabromidocuprate(II)
K2[Hg(SCN)4] potassium tetrathiocyanato-Smercurate(II)
K2[Zn(NCS)4] potassium tetrathiocyanato-Nzincate(II)
[Co(NH3)6]Cl3 hexaamminecobalt(III) chloride
[Pt(NH3)4] [PtCL4] tetraammineplatinum(II) Tetrachloridoplatinate(II)
[PtCl2(NH3)2] cis - and trans -diamminedichloridoplatinum(II),
[(NH3)4Co(OH)(NH2)Co(NH3)4]Cl4 μ-amido-μ-hydroxidobis[(tetramminecobalt(III)] chloride
[(NH3)3Co(OH)3Co(NH3)3]3+ tri-μ-hydroxidobis[(triamminecobalt(III)]
[(NH3)5Co–O2–Co(NH3)5](NO3)5 μ-superoxidobis[(pentaamminecobalt(III)] nitrate
[Ru(PPh3)3Cl3] mer- and fac-trichloridotris(triphenylphosphine)ruthenium(III)
Mn2(CO)10 bis(pentacarbonylmanganese) (Mn–Mn)

9. ISOMERISM
Compounds having same molecular formula but different structural arrangements called isomers
and this phenomenon known as isomerism. Because of complicated formulae of coordination
compounds many types of bonds and shapes are possible and therefore, these compounds show
many types of isomerism.
A. STRUCTURAL ISOMERISM
They differ in connectivity of ligands. These are various types:
(I) Polymerization Isomerism: These isomers have same empirical formula but different
molecular weights.
e.g. (1)

(2)

(II) Ionization Isomerism: This is due to exchange of ligands between the complex ion and ions
outside it. These isomers gives different ions in the solution.

(III) Hydrate Isomerism: This is special kind of ionization isomerism in which H2O molecule
replaces other ligands.

(IV) Linkage Isomerism: This occurs when there is ambidentate ligand in the complex.

(V) Coordination Isomerism: This occurs because of ligand exchange between cation and anion
complexes.
(VI) Coordination Position Isomerism: This occurs because of ligand interchange between
different metal nuclei of a polynuclear complex.

B. STEREOISOMERISM
This occurs because of different orientations of ligands in the space. There are two types of
stereoisomerism (i) Geometrical Isomerism and (ii) Optical Isomerism.
Stereoisomerism in Complexes with Coordination Number 4: Two principal geometries are
possible for complexes with C.N. 4: Tetrahedral and Square Planar
Tetrahedral Complexes
 Geometrical isomerism: This is not possible because all four ligands are adjacent to each other.
 Optical Isomerism: If plane of symmetry and center of symmetry are absent then complex may
be optically active.
Optical isomerism is possible only in those tetrahedral complexes in which central metal atom is
bonded with four different ligands and such complex called as asymmetric.
Square Planar Complexes
Geometrical Isomerism

Optical Isomerism: Optically inactive because of plane of symmetry (molecular plane)

Stereoisomerism in Complexes with Coordination Number 5

The complexes with coordination number 5 are less common but recently interest has been
increased rapidly. Regular and distorted trigonal bipyramidal (TBP) and square pyramidal (SP)
geometries are shown by these complexes. The energy difference between TBP and SP is very
small. Hence, one geometry easily converted to another which gives the condition of polytopal
isomerism. For example [Ni(CN)5]3- can adopt either TBP or SP geometry.
Cis- and trans-isomerism is also possible.

Stereoisomerism in Complexes with Coordination Number 6: Geometrical and optical Isomerism

Further Reading:
1. Concise Inorganic Chemistry, J.D. Lee
2. Inorganic Chemistry, J.E. Huheey, E.A. Keiter and R.L. Keiter,