Logic Institute Class: XI I Sub: Inorganic Chemistry

Chapter: Coordination Compounds

- Strive for Excellence

Coordination Compounds:
One Central metal atom/ion is surrounded by no. of oppositely charged ions or neutral molecules (ligands). Bond
between metal and ions/molecules is coordinate bond.

Werner’s Theory of Coordination Compounds: Two types of valence: (A) Primary and (B) Secondary Valence
Sr. No Primary Valence Secondary Valence
1 Principal Valence or Ionisable Valence Auxiliary Valence or Non-Ionisable valence
2 Oxidation State Coordination Number
Outer Sphere/Ionisable Sphere loosely bound, Inner Sphere/Coordination sphere – Strongly
3
separated easily attached, not separated from metal
4 Non-rigid, non-directional Have directional properties
5 Outside [ ] Inside [ ]
6 Always satisfied

Experimental observations of Werner’s Theory

Werner observed that Secondary Valence of a metal is always satisfied. This was confirmed when he took 4 different
compounds and reacted them individually with Excess AgNO3.
Four compounds were: CoCl3.6NH3 , CoCl3.5NH3 , CoCl3.4NH3 , CoCl3.3NH3
No. of ions precipitated No. of ions formed No. of serving dual Purpose Coordination
Compound on reaction with AgNO3 i.e. Prim as well as Sec Valence Compound
CoCl3.6NH3 3 Cl ions Four : 1 [Co(NH3)6] &3+ No Cl serves dual purpose [Co(NH3)6]Cl3
3 Cl ions
CoCl3.5NH3 2 Cl ions Three : 1 [Co(NH3)5Cl]2+ One Cl serves dual purpose [Co(NH3)5Cl]Cl2
& 2 Cl ions
CoCl3.4NH3 1 Cl ions Two : 1 [Co(NH3)4Cl2]+ Two Cl serves dual purpose [Co(NH3)4Cl2]Cl
& 1 Cl ions
CoCl3.3NH3 No Cl ions Zero Three Cl serves dual purpose [Co(NH3)3Cl3]

Ligands (Greek word ligane means ‘to bind’)

Mono or unidentate Poly or multidentate ligand Ambidentate ligand
Ligand
Only one donor More than one donor atom Two or more donor atoms but only one donor atom
atom is attached to the metal
eg. NH3, H2O, C , eg. (en) : Ethylene diamine (Bidentate) eg. –CN, –NC
Cl , CO –SCN, –NCS
E T : Ethylene Diamine Tetra –NO2, –ONO
Acetate (Hexadentate)

Homoleptic & Heteroleptic Complexes

Homoleptic Complex – Only one kind of donor group eg. [Co(NH3)6]3+
Heteroleptic Complex – More than one kind of donor group eg. [Co(NH3)4Cl2]+

Difference between Double Salts and Coordination Compounds:

Double salts dissociate completely into constituent ions when dissolved in water eg. Mohr’s Salt: FeSO4.(NH4)2SO4.6H2O
dissociates into Fe2+, ,S ions.
Coordination Compounds do not dissociate completely into constituent ions; only counter ions dissociate, coordination
entity does not dissociate eg. [Co(NH3)6]Cl3 dissociate into one [Co(NH3)6]3+ ion & three Cl ions.

Sidgwicks’ Electronic Theory – Sidgwick introduced a new concept of coordination bonding in which the ligands donate
the electron pair to the central metal atom and forms coordinate bond.
 Logic Institute Class: XI I Sub: Inorganic Chemistry
Chapter: Coordination Compounds
- Strive for Excellence

Effective Atomic Number (EAN) – Denotes the total number of electrons around central metal atom in a coordination
compound. Usually, a metal accepts e till the number of e becomes equal to the at. no. of the next rare gas atom.
For eg. Ni, Fe, Co, Zn will usually have 36 as EAN. There are certain exceptions.
EAN = Z – X + Y
where, Z = Atomic number of metal
X = No. of e lost during formation of metal ion (Oxidation Number)
Y = No. of e donated by ligands

IUPAC Nomenclature: (Go through Textbook examples)

Valence Bond Theory

Type of Hybridisation Geometry
sp Linear
sp2 Trigonal planar/ Triangular
sp3 Tetrahedral
dsp2 Square planar
sp3d / dsp3 Trigonal Bipyramidal
sp3d2 / d2sp3 Sqaure Bipyramidal / Octahedral
sp3d3 / d3sp3 Pentagonal Bipyramidal

Procedure to find hybridisation, Geometry, Magnetic Property, Inner or Outer complex, High or Low spin
1. Find electronic configuration of central metal atom
2. Find electronic configuration of central metal atom with oxidation state
3. Check whether Ligand is strong or weak. If strong Ligand is present (i.e either NH3 or C or CO) then push the
electrons in the inner orbitals. If ligand is weak, don’t push any electrons.
Examples
Sr. Compound Strong Hybridisation Geometry Magnetic Inner / Outer High Spin /
No. Ligand? Property complex? Low Spin
1 [Ni(CO)4] Yes sp3 Tetrahedral Diamagnetic Inner Low
2 iCl No sp3 Tetrahedral Paramagnetic Outer High
3 i(C ) Yes dsp2 Square Planar Diamagnetic Inner Low
4 [Cu(NH3)4]2+ Yes dsp2 Square Planar Paramagnetic Inner Low
5 [Co(NH3)6]3+ Yes d2sp3 Octahedral Diamagnetic Inner Low
6 [CoF6]3- No sp3d2 Octahedral Diamagnetic Outer High

Limitations of VBT:
1. Does not explain colour
2. Does not explain why some are inner complexes and some are outer complexes for same metal ion
3. Does not explain the thermodynamic stabilities
4. Does not distinguish between weak field and strong field ligands
5. Cannot predict exactly the tetrahedral and square planar structure of 4 – coordinate complex

Crystal Field Theory:

Five d-orbitals namely, dxy, dyz, dzx, d ,d . Of these 5 orbitals,
3 orbitals dxy, dyz, dzx are in between the axes (t2g group)and
2 orbitals d , d are along the axes (eg group)
1. Octahedral Complexes:
Ligands in octahedral complexes are along the axes. d-orbitals which are along the axes (d ,d )
experience more repulsion. Thus, while splitting, eg group goes up and t2g group goes down.
 Logic Institute Class: XI I Sub: Inorganic Chemistry
Chapter: Coordination Compounds
- Strive for Excellence

2. Tetrahedral Complexes:
Ligands in tetrahedral complexes are in between the axes. d-orbitals which are in between the axes (dxy, dyz,
dzx) experience more repulsion. Thus, while splitting, t2g group goes up and eg group goes down.

Spectrochemical Series
Spectrochemical series gives information about the relative strength of the ligands.
CO > C > en > NH3 > EDTA > NCS > H2O > > > S > Cl > r > I

Pairing of d4 electron depends on and P (P is energy required to pair 2 against electron-electron repulsion
in the same orbital). There are two options for d4 electron:
i. When > P, i.e. strong field ligand :- d4 electron goes to t2g
ii. When < P, i.e. weak field ligand :- d4 electron goes to eg

Stability of Coordination compounds: Two Factors:

1. Charge density of central metal atom: Higher the charge density, higher will be the stability
Charge density = ratio. eg. Cu > i > Co > e > Mn > Cd

2. Nature of ligand :- Stronger the ligand, Higher will be the stability

Applications of Coordination Compounds:

1. In the extraction of metals: (Leaching of Ag and Au using KCN or NaCN solution)
2. Biological importance:
a. Mg in Chlorophyll b. Fe in Haemoglobin c. Co in Vitamin B12
3. Cisplatin [PtCl2(NH3)2] used in the treatment of cancer
4. EDTA is used in estimation of hardness of water

ISOMERISM

Steroisomerism Structural

Geometrical Optical Hydrate

Ionisation Linkage Coordination
(cis or trans) (d or l) (Solvate)
 Logic Institute Class: XI I Sub: Inorganic Chemistry
Chapter: Coordination Compounds
- Strive for Excellence

±
[Ma b ]n
eg. [Pt(NH3)2Cl2]
cis and trans

±
[Ma bc n
eg. [Pt(NH3)2ClBr]
cis and trans
Square Planar Complexes
(4 Coord. comp.) ±
[Mabcd]n
eg. [Pt(NH3)(Py)ClBr]
3 isomers

±
[M( ) n
eg. [Pt(gly)2]; gly is glycino (bidentate)
cis and trans

GEOMETRICAL Tetrahedral
ISOMERISM No Geom Isomerism
(4 Coord. Comp.)

± ±
[Ma 6 ]n and [Ma 5 b]n
No Geom isomerism

±
[Ma b n
eg. [Co(NH3)4Cl2]
cis and trans
Octahedral
(6 Coord. comp.)
±
[Ma 3 b3 n
eg. [Cr(NH3)3Cl3]
fac and mer

±
[M( ) a n
eg. [Co(en)2Cl2]
cis and transr
 Logic Institute Class: XI I Sub: Inorganic Chemistry
Chapter: Coordination Compounds
- Strive for Excellence

Square Planar Complexes Symmetrtic

(4 Coord. comp.) 𝐍𝐎 𝐎𝐏𝐓𝐈 𝐀𝐋 𝐈𝐒𝐎𝐌𝐄𝐑𝐈𝐒𝐌

Complexes are weak, difficult to

Tetrahedral resolve into d and l form
(4 Coord. Comp.) 𝐍𝐎 𝐎𝐏𝐓𝐈 𝐀𝐋 𝐈𝐒𝐎𝐌𝐄𝐑𝐈𝐒𝐌
OPTICAL ISOMERISM
(Molecule should be If Complex contain only
unsymmetric i.e. chiral) MONODENTATE ligands, then
𝐍𝐎 𝐎𝐏𝐓𝐈 𝐀𝐋 𝐈𝐒𝐎𝐌𝐄𝐑𝐈𝐒𝐌

±
[M( )3 n
eg. [Co(C2O4)3]3- or [Co(en)3]3+
d and l form
Octahedral
(6 Coord. comp.) ±
[M( ) a2 n
eg. [Co(en)2Cl2]2+
cis is unsymmetrc :- d and l form
trans is symmetric :- no optical iso.

±
[M( ) ab n
eg. [Co(NH3)(en)2Cl]2+
d and l form

STRUCTURAL
ISOMERISM

Ionisation Linkage - (Only with Coordination Hydrate (Solvate)

Same formula but ambidentate)
Same formula but Same formula but differ in
produce different Same formula but interchange of ligands no. of H2O molecules inside
ions produce different between cationic & anionic & outside the coord. sphere
e.g. linkage of ligands complexes
e.g. [Cr(H2O)6]Cl3 ,
[Co(NH3)5SO4]Br & e.g. [Co(NH3)5NO2]Cl2 e.g. [Co(NH3)6] [Cr(CN)6] & [Cr(H2O)5Cl]Cl2 . H2O &
[Co(NH3)5Br]SO4 and [Co(NH3)5ONO]Cl2 [Cr(NH3)6] [Co(CN)6] [Cr(H2O)4Cl2] . 2H2O