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CO ORDINATION COMPOUNDS
co ordination compounds / complexes: these are the compounds in which central atom
(generally belonging to the d block elements) is associated with the ligands (neutral molecule
or anion ) by co ordinate bonds . ex. Chlorophyll, haemoglobin and vitamin B12 are
co ordination compounds of Mg, Fe, Co respectively.
Variety of metallurgical processes, industrial catalyst and analytical reagent involve use of
co-ordination compounds.
Alfred Werner is called father of coordination compound / chemistry because of his great
contribution in this field.
Postulates of Werner’s theory
i) In co-ordination compounds metal show two types of linkage /valency namely
primary valency and secondary valency.
ii) Primary valency is normally ionisable and are satisfied by negative ion/anions
iii) Secondary valency is non ionisable and are satisfied by neutral molecule /negative
ions, sec. valency is equal to co-ordination number and is fixed for a metal
Now a days primary valency is called oxidation no. and secondary valency is
called co ordination no.
iv) Secondary linkage to the metal has characteristic spatial arrangements
corresponding to different co-ordination no. such spatial arrangements are called
co-ordination polyhedra. Octahedral, tetrahedral and square planar geometrical
shapes are more common in co ordination compounds of transition metals
On the basis of following observation made with aqueous solution assign secondary
valences to metal in following compounds
Formula moles of AgCl precipitated answer
pdCl2.4NH3 2 [Pd(NH3)4]Cl2
NiCl2.6H2O 2 [Ni(H2O)6]Cl2
PtCl4.2HCl 0 [PtCl6(HCl)2]
CoCl3.4NH3 1 [Co(NH3)2Cl]Cl
PtCl2.2NH3 0 [Pt(NH3)2Cl2]

Differentiate b/w co ordination compounds and double salt

Co-ordination compound Double salt
The constituent atom or ion do not lose The constituent atom or ion loses their
their identity in aqueous solution identity in aqueous solution
Both primary and secondary valency are Only primary valency is involved
involved
Ex K4[Fe(CN)6 FeSO4.(NH4)2SO4.6H2O
Some definitions
1) Central metal atom: it is the metal atom generally belonging to d block element
which accommodate lone pair of electrons from the ligands in its vacant orbitals
leading to formation of co-ordinate bond. this central metal atom also acts as Lewis
acid as it can accept pair of electron.
2) Ligand: these are electron rich species (neutral molecule or anion) which place their
pair of electrons in the vacant d orbital of central metal atom during formation of co
ordinate bond.
Ligands could be of many types such as
i) Unidentate ligands: ligands with single donor atoms ex. Cl-,H2O,NH3
ii) Didentate ligands: when ligands could bind through two donor atoms ex.
CH2NH2-CH2NH2
iii) Polydentate ligands: when ligands could ligate through more than two donor
atoms ex. EDTA.
3) Chelate: when didentate or polydentate ligand uses two or more donor atom
simultaneously to bind to single metal atom a cyclic or closed ring structure is formed
which is called chelate and the phenomena is called chelation.
No. of ligands taking part in chelate formation is called denticity for ex. Denticity of
ethylene diamine is 2, EDTA is 6
4) Ambidentate ligands: ligands which have two different donor atoms in it ex. CN and
NC, NO2 and ONO, SCN and NSC.
5) Co ordination no. no. of ligand donor atoms which are directly attached to the central
metal atom. When a ligand gets attached to the central metal atom only sigma bond in
used in finding co ordination no. pi bond is not considered while deciding co-
ordination no.
6) Co ordination sphere:the part enclosed inside the square bracket in co ordination
compound is called co ordination sphere .
7) Co ordination polyhedron : the spatial arrangement of ligand around central metal
atom. The most common type of co ordination polyhedron are square planar ,
octahedral and tetrahedral.
8) Oxidation no. oxidation no. of central metal atom is the charge it would carry if all the
ligands are removed along with electron pair that are shared with central atom .
oxidation no. is represented by roman numeral in common bracket.
9) Homoleptic complex: the complexes in which only one type of ligand is present ex.
[Co(NH3)6]3+
10) Heteroleptic complex: the complexes in which more than one type of ligands are
present . [Co(NH3)4Cl2]+

Rules of writing the formula of co ordination compounds

i) Central atom is listed first
ii) Ligands are listed in alphabetical order after the metal
iii) Polydentate ligands are listed in alphabetical order .in case of abbreviated
ligands first letter of abbreviation is used to determine the position of ligands
in alphabetical manner
 iv) The formula of entire co ordination entity is enclosed in square bracket , when
ligands are polydentate their formula are enclosed in common bracket ,ligand
abbreviation are also enclosed in common bracket
v) When formula of co ordination entity is written without counter ion the charge
is indicated outside the square bracket as right superscript
vi) Charge on cation is balanced by the charge on anion

Limitations of Werner’s theory

Werner could not ans following questions
i) why only certain elements have remarkable property of forming co
ordinate bonds
ii) why co ordinate bonds have directional property
iii) why co ordinate bond have characteristic magnetic and optical
property.
Valence bond theory
According to valence bond theory metal atom under influence of ligands can use its (n-1)d ,
ns, np orbital for hybridisation to yield equivalent orbital of definite geometries such as
[Co(NH3)6]3+ octahedral (d2SP3 ) diamagnetic low spin /inner orbital
[CoF6]3- octahedral (SP3d2) paramagnetic high spin /outer orbital
[NiCl4]2- tetrahedral (SP3) paramagnetic
[Ni (CO)4] tetrahedral (SP3) diamagnetic
[Ni(CN)4]2- square planar (dSP2) diamagnetic
Limitations of VBT:
i) it involves no. of assumptions
ii) it does not give quantitative interpretation of magnetic data
iii) it does not explain color exhibited by co ordinate compound
iv) it does not give quantitative interpretation of thermodynamics and kinetic stability
of co ordination compound
v) it does not give exact interpretation about tetrahedral and square planar complexes
vi) it does not distinguish b/w weak field and strong field ligands .

crystal field theory (CFT)

crystal field theory is electrostatic model which considers metal ligand bond to be ionic
arising from purely electrostatic interaction b/w metal ion and ligands.
When the ligand attacks the central metal atom the degeneracy of d sub shell is broken and
the d subshell splits into two parts, the type of splitting depends on the type of complexes i.e
octahedral or tetrahedral complexes.
In case of octahedral complexes the d subshell splits into two parts namely t2g with lower
energy ( 2/5) and eg with higher energy ( 3/5)
The separation b/w the the t2g and eg orbital depends on the strength of ligand and the
strength of ligand can be decided by the position of ligand in electrochemical series
I-<Br-<SCN-<Cl-<S2-<F-<OH-<C2O42-<H2O<NCS-<edta4-<NH3<en<CN-<CO
The pairing of electrons in t2g orbitals in decided by the value of energies of CFSE and
pairing energy .
i) CFSE<P the fourth electron will just to eg orbital leading to ec t2g3 eg1 resulting
into high spin complexes and the ligand is weak field ligands like
cl-,I-,F-,OH-,H2O
ii) If CFSE>p the forth electron pairs up in t2g orbital leading to diamagnetic low
spin complex and the ligand is stron field ligand like NH3,en,CN-,CO
Note : d4 to d7 co ordination are more stable for strong filed as compared to weak field
ligand
Crystal field splitting in tetrahedral complexes

Rules for writing iupac names of co ordination compounds

1) Order of naming: cation, ligands (in alphabetical order), metal atom , anion.
2) Ligand name: written in alphabetical order. In anionic ligands ending with ide ,ite,
ate e is replaced by O ex. Flourido,chlorido , NO2- nitrito-N, ONO- nitrito-O ,
sulphato ,hydroxido, oxalato, cynido , acetato, thiocyanato , O22-peroxo , N3- nitrido ,
P3- phosphido.
Positive ligands end in ium
NO+ nitrosonium
NH2NH3+ hydrazinium
NO2+ nitronium
 Neutral ligands are named as such
CH3NH2 methylamine
NH2CH2CH2NH2 ethylenediamine
C5H5N pyridine
(C6H5)3P triphenylphosphine
PH3 phosphine
Some ligands have special names
H2O aqua
NH3 ammine
NO nitrosyl
CO carbonyl
When name of ligands indicate numerical prefix then prefix bis , tris , tetrakis are used as
prefix ex. [NiCl2(Pph3)] dichloridobis( triphenylphosphine)nickel (II)
When complex is anionic name of central atom ends in ate . for cationic and neutral ligand
there is no special ending for the metal atom
Ex. [Co(NH3)]Cl3 hexaamminecobalt (III) chloride
K[ptCl5(NH3)] potassium amminepentachloridoplatinate(III)
[Co(SCN)4]2- tetrathiocyanitocobaltate (II)

Some special name of anionic ligands metal atom

Fe ferrate ; Cu cuprate ; Ag argenate ; Au aurate ; Sn stannate .
Formula Name
K[Ag(CN)2 ] Potassiumdicyanidoargentate (I)
[PtCl(NO2)(NH3)4]SO4 Tetraamminechloridonitrito-N-platinum(IV)
sulpahte
K2[HgCl4] Potassiumtetrachloridomercurate(II)
[CoCl2(NO2)(NH3)3] Triamminedichloridonitrito-N-cobaltate (II)
K[PtCl3(NH3)] Potassiumammnetrichloridoplatinate (II)
[Ni(H2O)2(NH3)4]SO4 Tetraamminediaquanickel(II) sulphate
Na[Au(CN)2] Sodiumdicyanidoaurrate(I)
K3[Fe(CN)5NO] Potassiumpentacyanidonitrosylferrate(II)
K3[Fe(C2O4)4] Potassiumtetraoxolatoferrate(III)
K4[Ni(CN)4] Potassium tetracyanidonickelate (0)
[Cr(pph3)(CO)5] Pentacarbonyltris(triphenylpyridine)chromium
[{(C6H5)3P}3Rh]Cl Tris(triphenylpyridine)rhodiumchloride
[CoBr2(en)2Cl] Dibromidochloridobis(ethane-
1,2diamine)cobaltate(III)
HYBRIDISATION IN COORDINATION COMPOUNDS :-
(1) ¿
Co (27) = _______________ 4s23d7
3+ ¿¿
Co = _______________ 3d6
3d 4s 4p
∵ NH3 is strong field ligand so it will induce pairing in 3d e- so two 3d orbital will get vacant
Now two 3d one 4s three 4p orbital shall mix up to form six d2sp3 hybrid orbital which are
then occupied by six lone pair e- from NH3 to form ¿

¿=

↑↓ ↑↓ ↑↓
× × × × × ×Six d sp 2 3
hybrid
orbital
Characteristics of compound ¿
(1) d2sp3 hybridisation
(2) Low spin /inner orbital complex
(3) Diamagnetic
(4) Octahedral geometry

(2) [ CoF6 ]3-

Co (27) = ________ 4s23d7
O.N. of Co in [ CoF6 ]3- Co + 6F = -3 Co = -3+6 = +3
Co + 6(-1) = -3
Co3+=_________3d6
3d 4s 4p 4d
−¿¿
Since F is weak field ligand it will not induce pairing so

To accommodate lone pair of ligand one 4s , three 4p & two 4d orbital mix up to form six s
3 2 −¿¿ −¿¿
p d hybrid orbital which are then accommodated by six lone pair of e from F to form
[ Co F6 ]3-
[ Co F6 ]3- =
3d 4s 4p 4d
||

× × × × × ×
3 2
Six sp d hybrid orbital
Characteristics of compound [ Co F6 ]3-
(i) sp3d hybridisation
(ii) High spin / Inner orbital complex
(iii) Paramagnetic
(iv) Octahedral geometry

(3) [NiC l 4 ]2−¿ ¿

Ni (28) = ___________ 4 s2 3 d 8

O.N of Ni in [NiC l 4 ]2−¿ ¿ is Ni + 4Cl = -2

Ni + 4(-1) = -2
Ni = +2
Ni2+ = ______________ 3d8
3d 4s 4p
∵ Cl−¿ ¿ is weak field ligand it will not induce pairing So to accommodate e−¿¿ pair from Cl−¿ ¿
one 4s , three 4p orbital mix up to form four s p3 hybrid orbitals leading to formation of
2−¿ ¿
[NiC l 4 ]
2−¿ ¿
[NiC l 4 ] =
× × × ×

Characteristics of [NiC l 4 ]2−¿ ¿

(i) sp3 hybridisation

(ii) Tetrahedral geometry
(iii) High spin / outer orbital complex
(iv) Paramagnetic
(4) [Ni (CO)4]
Ni (28) = _________ 4s23d8
O.N of Ni in [Ni (CO)4] is Ni + 4(Co) = 0
Ni + 4(0) = 0 => Ni = 0
Ni = ____________
3d 4s 4p
∴ Co is strong field ligand so it will induce pairing on e in 3d by transfer of e from 4s
- -

Now one 4s & three 4p orbital shall mix up to form four sp 3 hybrid orbitals which
accommodate four lone pair of e- from Co to form [Ni (CO)4]

[Ni (CO)4] =
× × × ×
Four sp3 hybrid orbital
Characteristics of [Ni (CO)4]
 s p3 hybridisation
 Low spin complex
 Diamagnetic
 Tetrahedral

(5) ¿

Ni (28) = __________ 4s23d8

3d 4s 4p
∵ CN is strong field ligand so it will induce pairing on e- in 3d making one 3d orbital vacant ,
now one 3d , one 4s & two 4p orbital mix up to form four dsp2 hybrid orbital which are then
occupied by lone pair of e- from CN- to form ¿
¿=
× × × ×
Four dsp2 hybrid orbital
Characteristics

 dsp2 hybridisation
 Low spin complex
 Square planar geometry
 Diamagnetic

Try some other examples

(I) ¿ (II) [Fe F 6 ]3−¿¿ (III) ¿ (IV) [CoCl 6 ]3−¿¿