CHAPTER 9 CO-ORDINATION COMPOUNDS 7 marks

Coordination compounds - Introduction, ligands, coordination number, colour,

magnetic properties and shapes, IUPAC nomenclature of mononuclear
coordination compounds. Bonding, Werner's theory, VBT, and CFT; structure
and stereoisomerism, the importance of coordination compound[ds (in
qualitative analysis, extraction of metals and biological system).

Chlorophyll is the complex of Mg, Hemoglobin is the complex of Fe,

Vitamin B12 is the complex of cobalt.
The coordination compounds contain a central metal atom or ion
surrounded by a number of oppositely charged ions or neutral
molecules more than its normal valency.
For example: When aqueous ammonia is added to green solution of
nickel chloride, NiCl2, the colour changes to purple. The Ni2+ ions
almost disappear from the solution. The solution on evaporation,
yields purple crystals corresponding to the formula [Ni(NH3)6]Cl2.

1
Such a compound is called coordination (or complex) compound.
The properties of the complex compound are completely different
from those of Ni2+ ions or ammonia molecules.
NiCl2 + 6NH3 → [Ni(NH3)6]Cl2
When the compound is dissolved in water, it ionizes to give a new
species [Ni(NH3)6]2+ Such an ion is called complex ion.
[Ni(NH3)6]Cl2 → [Ni(NH3)6]2+ + 2Cl–
At this stage, it may be noted that the species in the square
brackets does not ionise. It remains as single entity. It is known as
complex entity.
Double Salts

Double salts are addition compounds which are formed by two

different saturated compounds but they lose their identity when
dissolved in water. In these compounds the individual properties of
the constituent ions are not lost.

e.g., Mohr’s salt, [FeSO4(NH4)2SO4.6H2O get dissociated into Fe2+,

NH4+ and SO42- ions.

Potash alum, K2(SO4).Al2(SO4)3.24H2O→ 2K+ + 2Al3+ + 4(SO4)2-

dissociates in water,

Carnallite : KCl.MgCl2.6H2O

On the other hand, the coordination compounds retain their

identities in the solid state as well as when dissolved in water or
any other solvent. Their properties are completely different from the
constituents.
For example, [Ni(NH3)6]Cl2 does not show the properties of NiCl2 or
ammonia even if it is formed from NiCl2 and NH3.

[Ni(NH3)6]Cl2 splits into [Ni(NH3)6]2+ + 2Cl– in water.

2
Terms Related to Coordination Compounds

1. Complex ion or Coordination Entity

It is an electrically charged species in which central metal atom or

ion is surrounded by a fixed number of ions or neutral molecules.
For example,[CoCl3(NH3)3] is a coordination entity in which cobalt
is surrounded by three ammonia molecules and three chloride
ions. Other examples are [Ni(CO)4], [PtCl2 (NH3)2], [Co(NH3)6 ]3+
(i) Cationic complex entity It is the complex ion which carries
positive charge. e.g., [Pt(NH3)4]2+

(ii) Anionic complex entity It is the complex ion which carries

negative charge. e.g., [Fe(CN)6]4-

(iii) Neutral complex entity [Ni(CO)4]

2. Central Atom or Ion

The atom or ion to which a fixed number of ions or groups are

bound in a definite geometrical arrangement around it, is called
central atom or ion.
It is also referred as Lewis acid. e.g., in [NiCI2(H2O)4].
Ni is central metal atom. It is generally a transition element or
inner-transition element.

3
3. Ligands

Ligands are electron donating species (ions or molecules) bound to

the Central atom in the coordination entity.
These may be charged or neutral.
Ligands are of the following types:
• Unidentate It is a ligand, which has one donor site, i.e., the
ligand bound to a metal ion through a single donor site. e.g.,
H2O, NH3, etc.

• Didentate It is the ligand which can bind through two donor

atoms.

• Polydentate It is the ligand, which have several donor sites or

atoms. e.g., [EDTA]4- is hexadentate ligand. Ethylene diamine
tetraacetate.

• Ambidentate ligands These are the mono dentate ligands which

can ligate through two different sites, e.g., NO2-, SCN-, CN-etc.

4
 Chelating ligands

• Di or polydentate ligands, which uses two or more donor atoms to

bind a single metal ion and are known as chelating ligands.

• These ligands cause cyclisation around the metal atom and the
complex is called chelate complexes.

• chelate complexes tend to be more stable than similar complexes

containing unidentate ligands.

• More the number of chelate rings, more is the stability of complex.

• When chelation occurs entropy increases and the process become

more favourable. For example

[Ni(NH3)6]2+ is less stable than [Ni(en)3]2+ where NH3 is a

unidentate ligand and ‘en’ be a didentate ligand

Chelate effect: The complexes which are formed by chelating

ligands like ethylene diamine (en) , EDTA etc are more stable
than those formed by monodentate ligands such as H2O, NH3
etc. This stabilization of coordination compounds, due to
chelation is known as chelate effect.

4. Coordination Number

It is defined as the number of ligand donor atoms to which the

metal is directly bonded. That is number of the coordinate bonds (
sigma bonds) formed by central metal atom, with the ligands. The pi
bond formed between the metal atom and the ligand will not be
considered for this purpose.
5
e.g., in [PtCI6]2-, Pt has coordination number 6.

In the case of mono dentate ligands,

Coordination number = number of ligands
In polydentate ligands.
Coordination number = number of ligands x 2, for didentate
ligands.
∴ Coordination number = number of ligands x denticity
5. Coordination Sphere

The central atom or ion along with the non ionisable ligands
attached to it are enclosed in square bracket and is known as
coordination sphere. The ionisable group written outside the
bracket is known as counter ions. In K4 [Fe(CN)6], the coordination
sphere is [Fe(CN)6]4- and the counter ion is K+.
6. Coordination Polyhedron

The spatial arrangement of the ligands which are directly attached

to the central atom or ion, is called coordination polyhedron around
the central atom or ion.

7. Oxidation Number of Central Atom

The oxidation number of the central atom in a complex is the

charge it would carry if all the ligands are removed along with the
electron pairs that are shared with the central atom, is called
oxidation number of central atom.

6
e.g., [CU(CN4]3-, oxidation number of copper is +1, and represented
as Cu(I).
Types of Complexes 1. Homoleptic complexes

Complexes in which the metal atom or ion is linked to only one kind
of donor atoms( ligands), are called homoleptic complexes e.g.,
[Co(NH3)6]3+

2. Heteroleptic complexes

Complexes in which the metal atom or ion is linked to more than

one kind of donor atoms are called heteroleptic complexes e.g.,
[Co(NH3)4CI2]+
Effective Atomic Number (EAN)

This concept was proposed by Sidgwick. In a complex, the EAN of

metal atom is equal to the total number of electrons present in it.
EAN = Z – ON of metal + 2 * CN
(where, Z = atomic number of metal atom ON = oxidation number of
metal and CN = coordination number of complex)
An ion with central metal atom having EAN equal to next inert gas
will be more stable.
For Eg. EAN Of Fe(CO)5 = 26-0 + 2x5 = 36, (Kr) then the compound
is stable.
6.NAMES OF SOME COMMON LIGANDS

NEGATIVE LIGANDS CHARGE NEUTRAL LIGANDS CHARGE

CN- cyanido -1 NH3 Ammine 0

NC- isocyanido -1

Cl- Chlorido -1 H2 O Aqua 0

Br- Bromido -1 NO Nitrosyl 0

F- Fluorido -1 CO Carbonyl 0

7
 SO42- Sulphato -2 PH3 Phosphine 0

C2O42- Oxalato -2 CH2-NH2 (Ethane-1,2- 0

diamine)
CH2NH2

NH2- Amido -1 POSITIVELIGANDS

NH2- Imido -2 NH2-NH3+ Hydrazinium +1

ONO- Nitrito-O -1 NO+ Nitrosonium +1

NO2- Nitrito-N -1 NO2+ Nitronium +1

NO3- Nitrato -1

SCN- Thiocyanato-S -1

NCS- Isothiocyanato-N -1

CH2(NH2)COO- Glycinato -1

-OH Hydroxido -1

IUPAC Naming of Complex Compounds

Naming is based on a set of rules given by IUPAC.

1. Name of the compound is written in two parts (i) name of cation,
and (ii) name of anion.

2. The cation is named first in both positively and negatively

charged coordination complexes.

3. The dissimilar ligands are named in an alphabetical order before

the name of central metal atom or ion.
4. For more than one similar type of ligands, the prefixes di, tri,
tetra, etc are added before its name. If the di, tri, etc already
appear in the ligand, then the number of ligands are bis, tris,
tetrakis are used mainly for, if more than one type of di dentate
or poly dentate is present.

1.[NiCl2(PPh3)2] – Dichloridobis(triphenylphosphine)nickel(II)

8
5. If the complex part is anion, the name of the central metal ends
with suffix ‘ate’.

Cu- cuprate

Ag- argentate

Pb- plumbate.

Au-aurate

Hg - hydragerate

6.Names of the anionic ligands end in ‘0’, names of positive ligands

end with ‘ium’ and names of neutral ligands remains as such. But
exception are there, as we use aqua for H2O, ammine for NH3,
carbonyl for CO and nitrosyl for NO.

7. Oxidation state for the metal cation, anion or neutral coordination

compounds is indicated by Roman numeral in parentheses.

8. The name of the complex part is written as one word.

9. If the complex ion is a cation, the metal is named same as the

element.

10.The neutral complex molecule is named similar to that of the

complex cation.

Some examples of neutral complexes are

(i) [Cr(NH3)3(H2O)3]Cl3

triamminetriaquachromium (III) chloride

(ii) [Co(H2NCH2CH2NH2)3]2(SO4)3

tris (ethane-l,2-diamine) cobalt (III) sulphate

(iii) [Ag(NH3)2] [Ag(CN)2] diamminesilver(I) dicyanidoargentate(I)

(iv) K4 [Fe(CN)6]
9
potassium hexacyanidoferrate (II)

Page no 250

9.6 Using IUPAC norms write the formulas for the following:

(i) Tetrahydroxidozincate(II)
10
(vi) Hexaamminecobalt(III) sulphate
(ii) Potassium tetrachloridopalladate(II)
(vii) Potassium tri(oxalato)chromate(III)
(iii) Diamminedichloridoplatinum(II)
(viii) Hexaammineplatinum(IV)
(iv) Potassium tetracyanidonickelate(II)
(ix) Tetrabromidocuprate(II)

(v) Pentaamminenitrito-O-cobalt(III)
(x) Pentaamminenitrito-N-cobalt(III)
xi)Dichloridobis (ethane-1,2-diamine) platinum (IV) nitrate
Board 2022,2019,2015, 2020…
Ans: i)Zn(OH)4]2-
vi)[Co(NH3)6]2(SO4)3
ii)K2[PdCl4]
vii)K3[Cr(C2O4)3]
iii)[Pt(NH3)2Cl2]
viii) [Pt (NH3)6 ]4-
iv) K2[Ni(CN)4]
ix) [Cu(Br)4]2-
v) [Co(NH3)5 (ONO)]2+
x) [Co(NH3)5 (NO2)]2+
xi) [PtCl2(en)2] (NO3)2

WERNER’S THEORY OF CO-ORDINATIONCOMPOUNDS:

1.In co-ordination compounds metals show two types of

linkages(valencies) –primary or secondary

2.The primary valencies are nondirectional and are ionizable. They

are satisfied by –ve or + ve ions. The 10 valency corresponds to the
oxidation state of the metal atom.

11
3.The secondary valencies are directional and are non ionisable.
They are satisfied by neutral molecules, or negative ions. The 20
valency is fixed for a metal and it corresponds to the co-ordination
number of the metal.

4. The ions or groups bound by the 20 valency to the metal have

characteristic spatial arrangements, corresponding to the different
co-ordination numbers.

(1) CoCl3.6NH3 : Cobalt has primary valency (oxidation state) of three and
secondary valency (coordination number) six. Secondary valencies are
represented by thick lines (—) and primary valencies are shown by dotted lines
(….). In the complex, all the 6 secondary valencies are occupied by six NH3
molecules. The Cl¯ ions are bonded to Cobalt by three primary valencies. These
chloride ions are ionisable and therefore can be precipitated on the addition of
silver nitrate. The central metal ion and the neutral molecules or ions (ligands)
satisfying secondary valencies are written in a square bracket while writing the
formula of the complex compound.

Werner’s structure can be drawn for these molecules using bold

lines for secondary valency and dotted line for primary valency in
an octahedral manner.

CoCl3.6NH3 CoCl3.5NH3 CoCl3.4NH3

In a series of compounds of Cobalt (iii) chloride with ammonia ,

the chloride ions could be precipitated as Silver chloride by
adding silver nitrate solution.
12
The observations from one mole of the complex can be entered
in the table.

Werner’s colour No of Formula of Solution Total

formula mols the complex conductivity no.
of corresponding of
AgCl to ions
ppt

CoCl3.6NH3 yellow 3 [Co(NH3)6]Cl3 1:3 4

mol electrolyte

[Co(NH3)6]3+
+3Cl-

CoCl3.5NH3 purple 2mol [Co Cl 1:2 3

(NH3)5]Cl2 electrolyte

[Co Cl
(NH3)5]2+ + 2Cl-

CoCl3.4NH3 green 1 [Co Cl2 1:1 2

mol (NH3)4]Cl electrolyte

[Co Cl2
(NH3)4]+ +Cl-

CoCl3.4NH3 violet 1mol [Co Cl2 1:1 2

(NH3)4]Cl electrolyte

[Co Cl2
(NH3)4]+ +Cl-

13
1.[Pd(NH3)4]Cl2 2.[Ni(H2O)6]Cl2 3.[Pt(Cl)4(HCl)2]

4.[Co(NH3)4Cl2]Cl 5.[Pt(NH3)2Cl2]

What is the primary and secondary valencies of Cobalt in

[Co(en)3]3+

Secondary valency is 6 as ‘en’ is a didentate ligand.

Primary valency is x+0=3, x=3

Pg 264. que 9.2 FeSO4 solution mixed with (NH4)2SO4 solution in 1:1 molar
ratio gives the test of Fe2+ ion but CuSO4 mixed with aqueous ammonia in1: 4
molar ratio does not give test of Cu2+ ion. Explain why?

When FeSO4 and (NH4)2SO4 solution are mixed in 1:1 ratio, a double salt is
formed. It has the formula FeSO4 (NH4)2SO4 .6H2O. In aqueous solution, the
salt dissociates to form Fe2+, NH4+ and SO42- & H2O.

When CuSO4 and NH3 are mixed in the molar ration of 1:4 in solution, a
complex [Cu(NH3 )4]SO4 is formed. Copper ions are non ionizable.

14
[Cu(NH3)4]2+ SO42_

Isomerism in Coordination Compounds

Coordination compounds exhibit the following types of isomerism:

12. Stereoisomerism

Stereoisomers have the same chemical formula and chemical bonds

but they have different spatial arrangement. These are of two types-
(i) Geometrical isomerism Geometrical isomers are of two types
i.e., cis and trans isomers. This isomerism is common in complexes
with coordination number 4 and 6.

Geometrical isomerism in complexes with coordination

number 4 : (tetrahedral and square planar structures)
(i) Tetrahedral complexes do not show geometrical isomerism.
Geometrical isomerism arises in heteroleptic complexes due to the
different possible geometric arrangements of the ligands.
(ii) Square planar complexes of formula [MX2L2] (X and L are
unidentate) show geometrical isomerism. The two X ligands may be
arranged adjacent to each other in a cis isomer, or opposite to each
other in a trans isomer,

(iii) e.g., Cis-diamminedichloridoplatinum (11) is called Cisplatin

which is used in tumor treatment. Cis form is pale yellow where as
trans form is dark yellow in colour.

1-3,2-4 positions are trans and 1-2, 2-3,3-4 & 1-4 are cis positions.

(iv) Square planar complex of the type [MABXL] (where A, B, X, L,

are unidentate ligands) shows three isomers, two cis and one trans.

15
e.g., [Pt(NH3) (Br)(Cl)(Py)]. Keep the position of one ligand fixed and
placing the other ligands trans to it. These isomers will not exhibit
optical isomerism.

Geometrical isomerism cannot occur in complexes of the type MA4 , MA3B or

MAB3 because all possible spatial arrangements for any of these complexes will be
exactly equivalent.
Pg no 252 example 4 Que . Why is geometrical isomerism not
possible in tetrahedral complexes having two different types of
unidentate ligands coordinated with the central metal ion?
Tetrahedral complexes do not show geometrical isomerism because
the relative positions of the unidentate ligands attached to the
central metal atom are the same with respect to each other.
Geometrical isomerism in complexes with
coordination number 6

Octahedral complexes of formula [MX2L4], X& L are unidentate

ligands. The two X - ligands may be oriented cis or trans to each
other, e.g., [Co(NH3)4Cl2]+.

[CoC12(NH3)4] + Here 1 and 6, 2and 4, 3 and 5 are trans positions in

octahedral complexes.

16
Ii)Octahedral complexes of formula [MX2A2], where X are unidentate
ligands and A are didentate ligand. form cis and trans isomers, e.g.,
[CoC12(en)2]

iii)In octahedral complexes of formula [MA3X3], if three donor atoms

of the same ligands occupy adjacent positions at the corners of an
octahedral face. it is known as facial (fac) isomer, when the
positions are around the meridian of the octahedron, it is known as
meridional (mer) isomer. e.g., [Co(NH3)3(NO2)3]

17
How many EDTA molecules are required to make an octahedral
complex with a Ca2+ ion.?
EDTA is a hexadendate ligand therefore only one EDTA molecule is
required to form octahedral complex with Ca2+ion
Page no 252

(ii) Optical isomerism These are the complexes which have chiral
structures. No chiral centre. It arises when mirror images cannot be
superimposed on one another. These object and the mirror image
are called enantiomers. The two forms are called dextro (d) and
laevo (l) forms.
Tetrahedral complexes with formula [M(AB)2] show optical isomers.
Square planar complexes do not show optical isomers as they
contain a plane of symmetry.
The cis isomer of octahedral complexes exhibit optical isomerism.

18
Optical isomerism is common in octahedral complexes involving
two types of uni dendate ligands.
Example cis- [Co(NH3)4Cl2]+
Another example : MX2A2 type which contains two uni dentate and
two didentate ligands.
Example. [PtCl2(en)2]2+ Cis isomer only exhibits optical isomerism.

When one of the ligand is di dentate and the other 4 are uni
dendate. Eg. [Co(en)(NH3)4]3+ can also exhibit optical isomerism.
HW draw the isomers.

Optical isomers (d and l) of [Co(en)3]3+

19
2.Structural Isomerism

In this isomerism, structures with the same molecular formula but

the isomers have different bonding pattern. Different types of
structural isomers are
(i) Linkage isomerism This type of isomerism is shown by the
coordination compounds having ambidentate ligands. e.g.,

[Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2 or pentaamminenitrito-

N- Cobalt (III) chloride and pentaamminenitrito-O -Cobalt (III)
chloride.
(ii) Coordination isomerism This type of isomerism arises from
the interchange of ligands between cationic and anionic complexes
of different metal ions present in a complex, e.g.,

[Cr(NH3)6] [Co(CN)6] and [Co(NH3)6] [Cr(CN)6]

(iii) Ionisation isomerism This isomerism arise due to the
interchange of groups between coordination sphere of the metal ion
and the counter ion.

20
(iv) Solvate isomerism Isomerism in which the solvent involved
acts as the ligand. This is also known as hydrate isomerism, when
water is the solvent. It has different number of water molecules in
the coordination sphere and outside.e.g..

[Co(H2O)6]Cl3 Hexaaquacobalt(III) chloride

[Co(H2O)5C1]Cl2·H2O Pentaaquachloridocobalt(III)
chloridemonohydrate.
[Co(H2O)4C12]Cl·2H2O Tetraaquadichloridocobalt(III)
chloridedihydrate
HW 31st august 2023. Intext question 9.3 & 9.4

Ans: i) a)Geometrical isomers- both cis & trans

b) Optical isomer is from the cis form. Must draw both enantiomers.
ii) Two optical isomers, draw both enantiomers as object & and its
mirror image.
iii)Linkage isomerism: [Co(NH3)5(NO2)](NO3)2 &,Co(NH3)5(ONO)](NO3)2
& ionization isomerism [Co(NH3)5NO2](NO3)2
and[Co(NH3)5NO3](NO2)(NO3)
iv) cis and trans isomers with respect to chloride ion
9.4 The complex which give white curdy precipitate with silver
Nitrate have counter ion as chloride and the complex which give
white precipitate with BaCl2 have sulphate as the counter ion.

21
Werner was the first to describe the bonding features in coordination
Compounds however fails to explain
i)Why only certain elements form coordination compounds?
(ii) Why the bonds in coordination compounds are directional?

(iii) Why coordination compounds are magnetic in nature?

Bonding in Coordination Compounds.

Valence Bond Theory (VBT)

This theory was proposed by L. Pauling in 1930 s.

VALENCE BOND THEORY:

Brief outline of this theory are:

1. A suitable number of vacant orbitals must be present on the

central metal atom for the formation of co-ordinate bonds with
suitable ligand orbitals.
2. Depending upon the number of bonds to be formed the central
atom or ion use appropriate number of atomic orbitals that is
s, p, d, for hybridization to form a set of equivalent orbitals.
3. (under the influence of the ligands the metal ion can use its

(n-1)d, ns, np or ns, np and nd- orbitals of the same shell for
hybridization.

4. The hybrid orbitals are allowed to overlap with those of ligand

orbitals that can donate an electron pair for bonding.
5. The outer orbital, (high spin), hypo ligated complexes are
formed when the d- orbitals of the outer shell is used.
6. Inner orbital,( low spin), hyper ligated complexes are formed
when the d- orbitals of the inner shell are used in
hybridization.

NUMBER OF ORBITALS & THE TYPES OF HYBRIDISATION

Co-ordination no. Type of geometry

Hybridisation

22
 4 Sp3 tetrahedral
4 dsp2 Square planar
5 Sp3d/ Trigonal bipyramid
5 dsp3 Trigonal bipyramid
6 Sp3d2 octahedral
6 d2sp3 octahedral

Examples to be done in the note book

Inner orbital complexes or outer orbital

complexes

When d-orbitals of (n – 1) shell are used, these are known as inner

orbital complex, they are formed due to strong field ligands or low
spin ligands and hybridisation is d2sp3. They are octahedral in
shape.

When outer d-orbital are used in bonding, the complexes are called
outer orbital complexes. They are formed due to weak field ligands
or high spin ligands and hybridisation is sp3d2. They have
octahedral shape.

6 – ligands (unidentate), octahedral entity.

4-ligands (unidentate) tetrahedral entity.

Spectrochemical series:

I− < Br−< SCN−<Cl−< S2− F−< OH−< C2O42−<H2O < NCS−< edta 4-

< NH3< en < CN−< NO2− < CO

Atomic number of Cobalt is 27: [Ar]4s2 3d7

Cobalt is in +3 oxidation state.
So the electronic configuration of Co3+ is [Ar]4s0 3d6 .
To accommodate 6 pairs of electrons from 6 NH3 molecules Co3+
provide six equivalent hybrid orbitals.

23
Since NH3 is a strong ligand, the 3d electrons paired up leaving
two d orbitals for d2sp3 hybridization.

Thus the complex is octahedral,

diamagnetic as the electrons in the metal ion are paired.
low spin or spin paired complex.
Since the inner d orbital (3d) is used in hybridization it is an inner
orbital complex
Explain [CoF6]3-is an outer orbital complex & a
high spin complex :

Atomic number of Cobalt is 27.

Cobalt is in +3 oxidation state.
So the electronic configuration of Co3+ is [Ar]4s0 3d6 .
To accommodate 6 pairs of electrons from 6 F- ligand,
Co3+ should provide six hybrid orbitals.
F- is a weak ligand, so the 3d electrons cannot be paired up. Thus,
two outer 4d orbitals are used for sp3 d2hybridization.

24
Thus the complex [CoF6 ] 3– is octahedral,
paramagnetic by the presence of unpaired electrons in the metal
ion,
As outer orbital (4d ) is used for hybridisation, it is an outer orbital
complex,
high spin or spin free complex.
HW intext questions 9.5,9.6, 9.7, 9.8,9.9

Explain the formation of [Ni(Cl)4]2- , [ Ni(CO)4] &

Ni(CN)4]2- ( 9.5 & 9.6 together)

Formation of [Ni(Cl)4]2- tetracholoridonickelate(II)

atomic number of Nickel is 28.

Nickel is in +2 oxidation state.
So the electronic configuration of Ni2+ is [Ar]4s0 3d8 .
25
To accommodate 4 pairs of electrons from 4Cl- ligand, Sinc Cl- is a
weak ligand, so the 3d electrons can not be paired up. Thus Ni2+
undergo sp3 hybridisation.

[Ni(Cl)4]2- is
tetrahedral, outer spin complex, high spin complex and
paramagnetic.
Formation of [ Ni(CO)4] Tetra carbonyl nickel(0)
In[ Ni(CO)4] Nickel is in zero oxidation state. The electronic
configuration of Ni(0) is [Ar]4s2 3d8
CO is a strong ligand, in presence of CO, the unpaired 3d- electrons
and the two 4s electrons make all the 3d orbitals to be paired. Thus
Ni(0) undergo sp3 hybridisation.

[Ni(CO)4 ] has tetrahedral geometry but is diamagnetic since nickel

is in zero oxidation state and contains no unpaired electron.
Explain [Ni(CN)4]2- (Tetracyanidonickelate(11)

Atomic number of Nickel is 28. Nickel is in +2 oxidation state. So

the electronic configuration of Ni2+ is [Ar]4s0 3d8 . To accommodate
4 pairs of electrons from 4CN- ligand, Ni2+ should provide four
equivalent hybrid orbitals. CN- is a strong ligand, so the 3d

26
electrons get paired up leaving one empty d orbital for
hybridization. Thus Ni2+ undergo dsp2 hybridisation.

[Ni(CN)4]2- is square planar, diamagnetic, low spin

complex. Inner orbital complex.

Sample paper 2022-23 que. No 27. Using Valence bond theory,

explain the following in relation to the paramagnetic complex
[Mn(CN)6] 3-
a.type of hybridization b. magnetic moment value c. type of
complex – inner, outer orbital complex
27.[Mn(CN)6] 3- Mn = [Ar] 3d54s2 Mn3+ = [Ar] 3d4
Mn (ground state)

27
Atomic number of Iron is 26.
In both complexes Iron is in +3 oxidation state.
So the electronic configuration of Fe3+ is [Ar]4s0 3d5
In presence of CN- , a strong ligand, the 3d5 electrons pair up
leaving only one unpaired electron. Weakly paramagnetic.
The hybridization is d2sp3 forming an inner orbital complex.
In presence of water, a weak ligand the 3d- electrons do not pair up.
The hybridization is sp3d2 forming an outer orbital complex
containing 5 unpaired electrons. Thus it is strongly paramagnetic.

In Pt (CN4) 2- ion, Atomic number of Pt is 78. Platinum is in +2

oxidation state. Electronic configuration is 5d8 . CN- is a strong
ligand 5d- get paired leaving one d orbital for hybrididation. It
undergo dsp2 hybridisation.

Before Hybridisation
After hybridization , no of unpaired electrons is zero.

28
 S.No Inner Orbital Complex Outer orbital complex
1. Strong field or low spin Weak field or high spin
ligands ligands

2. Hybridisation is dsp2 Hybridisation is sp3 (mixing

(mixing up of one 3d, one up of one 4s and three 4p
4s and two 4p orbitals are orbitals are involved)
involved)
Tetrahedral complex with
3. Square planar complex C.N 4
with C.N 4

The coordination number 4 shows the geometry can be either tetrahedral sp3 or
square planar dsp2.
The configuration of Mn2+ is 3d5
dsp2 can be observed by the involvement of inner d- electron which makes the
number of unpaired electrons of Mn2+ as 4.
where as that with sp3 the number of unpaired electrons will be 5.
With the magnetic moment value 5.9 BM the number of unpaired electrons
would be 5. Thus, the geometry of the complex be tetrahedral.

Limitations of VBT

1. It involves a number of assumptions.

2. It does not give quantitative interpretations of magnetic data.

3.It does not explain the colour exhibited by co-ordination

compounds.

4 It does not make exact predictions regarding the tetrahedral

and square planar structures of four co-ordinate complexes.

5. It does not distinguish between strong and weak ligands. And

the existence of outer orbital complex and inner orbital complex.

29
Crystal Field Theory (CFT)

This theory was proposed by H. Bethe and van Vleck. Orgel. in

1952, applied this theory to coordination compounds. In this
theory, ligands are treated as point charges in the case of anions
and dipoles in case of neutral molecules.

CRYSTAL FIELD THEORY: It is an electrostatic model which

considers the metal-ligand bond to be ionic which arises from
electrostatic interaction between the metal ion and the ligand.

POSTULATES:

1.The ligands are considered as point charges.

2. When the ligands approach central atoms or ions electrostatic

repulsion sets in between the d- electrons of the metal and the
excess electrons of the ligand

3. Due to the repulsive forces, energy of the d- orbitals increases

and two sets of d- orbitals- t2g and eg are formed

t2g set has three orbitals dxy, dyz and dxz and the

eg has two orbitals d(x2-y2) and dz2

CRYSTAL FIELD SPLITTING IN OCTAHEDRAL COMPLEXES

30
• The metal atom or ion have five degenerate orbitals.
• The six ligands approach the metal atom or ion along the three
axes.
• There will be repulsion between the electrons in the metal d-
orbital and the electrons of the ligands.
• The repulsion is more when the d- orbital is directed towards the
ligand than when it is away from the ligand.
• Thus d (x2-y2) and dz2 orbitals which point towards the axes
experience more repulsion and will be raised in energy that is (eg
orbitals)
• The dxy, dyz and dxz orbitals which are directed between the
axes will be lowered in energy relative to the average energy in
the spherical field (t2g orbitals)
• Energy of eg set of orbitals > energy of t2g set of orbitals.
• The splitting of degenerate levels due to the presence of ligands
in a definite geometry is called crystal field splitting. The energy
of separation between t2g and eg levels in an octahedral field is
octahedral crystal field splitting and can be represented by ∆o.
• The energy of eg orbitals will increase by (3/5) Δo and t2g will
decrease by (2/5) Δo.
• It depends on the field produced by the ligand and the charge on
the metal ion. Stronger the ligand, greater will be the splitting
between the orbitals.
• The electronic configuration in these orbitals depends on the
relative magnitude of the crystal field splitting ∆o and the

31
 pairing energy, P that is the energy required for pairing in an
orbital.
• Crystal Field Splitting energy: When the ligands approach
the transition metal ion, due to the force of repulsion between
the electrons, the degenerate d-orbitals split into t2g and eg and
the difference between their energy in a Crystal field is called
Crystal field splitting energy CFSE.

• In the case of octahedral field, it is Δo is called octahedral

crystal field splitting energy.

The arrangement of ligands in the increasing order of field

strength or in the increasing order of crystal- field splitting
energy (CFSE) is called spectro chemical series.

The ligands with large value of CFSE are present on the

R.H.S of the series are strong field ligands while that on the
L.H.S are weak field ligands with a small value of CFSE.
Also, strong field ligands cause higher splitting in the d
orbitals than the weak field ligands.

I− < Br−< SCN−<Cl−< S2− F−< OH−< C2O42−<H2O < NCS−< edta4- <
NH3< en < CN−< NO2− < CO

-NO2 ligand have more field strength than NH3 molecule.

If Δo < P, the fourth electron enters one of the eg orbitals giving the
configuration t2g3 e1g.

Ligands for which Δo < P are known as weak field ligands and form
high spin complexes.

If Δo > P, it becomes more energetically favourable for the fourth

electron to occupy a t2g orbital with configuration t2g4 eog. (where,
P = energy required for e- pairing in an orbital). Ligands which

32
produce this effect are known as strong field ligands and form low
spin complexes.

Explain the electronic configuration of complex species with d4

configuration with reference to

a) ∆o > P
b) ∆o < P

In the octahedral complexes, the d- orbitals split into two sets –

t2g with lower energy and eg with higher energy.

a) ∆o > P If the splitting energy is more than the energy required

for pairing up of electrons, as the lower energy is preferred,
Then the Electronic configuration will be t2g4 , eg0 . electrons
preferred to pair up. Ligands which produce this effect are
strong field ligands and form low spin complexes.
b) ∆o < P If the splitting energy is less than the energy required
for pairing up of electrons, then the fourth electron enters
into one of the eg orbital and the configuration will be t2g3,
eg1 . Such ligands are called weak field ligands and form high
spin complexes.

Crystal field splitting in tetrahedral complexes

In tetrahedral complexes, four ligands may be imagined to occupy

the alternate corners of the cube and the metal ion at the center of
the cube.
In such complexes d – orbital splitting is inverted and is smaller as
compared to the octahedral field splitting.
Orbital splitting energies are so low, so that pairing of electrons are
not possible. So tetrahedral complexes are of high spin complexes.
The ‘g’ subscript is used for the octahedral and square planar complexes which
have centre of symmetry. Since tetrahedral complexes lack symmetry, ‘g’
subscript is not used with energy levels.

33
• The metal atom or ion have five degenerate orbitals.
• When the central atom is surrounded by the ligand which has
excess of electrons, due to electrostatic repulsion between the
ligand and the d- orbitals, energy of the d- orbitals increases.
• In the tetrahedral complexes ligand approach the metal atom or
ion between the axes.
• In such complexes d – orbital splitting is reversed and is smaller
as compared to the octahedral field splitting.
• t2 has higher energy as the ligand approaches between the axes
in the tetrahedral complexes which experiences more forces of
repulsion.

• Energy of t2 set of orbitals > Energy of e- set of orbitals.

• For the same metal, the same ligands and metal- ligand
distances, ∆t = 4/9∆o
• The orbital splitting energies are not sufficiently large for forcing
pairing to takes place. Thus
• low spin configurations are rarely observed. Or only high spin
complexes are observed.

Why are low spin tetrahedral complexes not formed?

34
CBSE 2018, 2020

• ∆t = 4/9∆o

In tetrahedral complexes, the orbital splitting energies (∆t) are less,

and ∆t >P chances are less.

It would be always ∆t <P, thus forced pairing does not take place.
Number of unpaired electrons are more than the forced paired
electrons. therefore, low spin complexes are not formed.

Sample paper 2022.The CFSE of [CoCl6] 3- is 18000 cm-1 the CFSE for
[CoCl4]- will be:

• Ans. ∆t = 4/9∆o = 4/9 x 18000=8000

8000cm-1

What are the factors which determine the magnitude of the

orbital splitting energy?

1. Nature of the ligand

2. Oxidation state of the metal ion
3. Nature of metal ion
4. Geometry of co-ordination entity.

How the nature of the ligand affect the stability of a complex

ion?

The more basic a ligand, the greater the ease with which it can
donate its lone pairs of electrons and therefore the greater the
stability of the complexes formed by it. For anionic ligands, the
higher the charge and smaller the size, the more stable is the
complex formed.

COLOUR IN CO-ORDINATION COMPOUNDS

35
 • Generally CFSE (∆0), crystal field splitting energy is the same
as that of energy of a photon of visible light.
• Therefore a transition metal complex can absorb energy from
the visible light and excites the electron from a lower energy
d- orbital into the higher energy levels
• i.e., electron jump from t2g level to higher eg level.
• The colour of the complex is complementary to the amount of
energy absorbed
• The colour of a particular compound depends upon the
magnitude of Crystal field splitting which further depend on
the nature of the ligand.
• The ligands differ in their field strength and that decide the
crystal field splitting. The magnitude of splitting observed in
each case can be explained on the basis of spectrochemical
series.
• In the absence of ligands, crystal field splitting does not occur
and hence the substance is colourless
• When white light falls on the complex, some part of it is
absorbed. Higher the CFSE, lower will be the wavelength
absorbed by the complex. The observed colour of the complex
will be its complimentary colour. (that is the colour generated
from the wavelength left over).

Influence of the ligands on the colour of the complex:

NiCl3 is dissolved in water and the didendate (en) is progressively

added in the molar ratio 1:1, 1:2 and 1:3 the following reactions
takes place and associated colour changes occur.

36
Energy is inversely proportional to the wavelength. Violet color with
lower wavelength will have more energy associated with it.
[Ni(en)3]2+ is the stablest complex with didentate ligands.
[Ni(en)3]2+ be the more stable complex.

Explain the reason behind the colour of some gem stone with the
help of an example.
The colors of many gem stones are due to the presence of transition
metal ions & color are produced due to d-d transition. For example
the mineral corundum Al2O3 is colorless when pure but when
various M3+ transition metal ions are present in trace amounts
various gem stones are produced. Ruby is Al2O3 containing about
0.5- 1% Cr3+

37
Que [Ti(H2O)6]3+ is violet in colour. ( must draw the diagram)

It is an octahedral complex.
Here ‘Ti’ is in + 3 oxidation state.
A single electron is present in the t2g in the ground state of the
complex. t2g1, eg0
If light corresponding to the energy of blue- green is absorbed by
the complex, it would excites the electron from t2g level to the empty
eg level. ( t2g1, eg0 → t2g0,eg1 )
Consequently the complex appears with its complementary colour
of violet.
Thus the colour of the complex is due to d-d transition.

What happens when [Ti(H2O)6]3+ is heated strongly. Explain the

observation.
On heating the violet colour of the complex disappears.
Water molecules acting as ligands are removed.
Crystal field splitting of d- orbitals will not occur.
The unpaired electron cannot undergo d-d transition.
Thus the complex become colorless.
2+ 2−
.A solution of [Ni(H2O)6] is green but a solution of [Ni(CN)4] is
colourless. Explain.
ANS. In [Ni(H2O)6]2+, water, is a weak field ligand. Therefore, Ni2+
has 3d8 configuration. There are unpaired electrons present in
Ni2+. The d−d transition is possible by absorbing red light and its
complimentary color green will be radiated. Hence, Ni(H2O)6]2+is
coloured.
In[Ni(CN)4]2−, Ni is in +2 oxidation state with 3d8 configuration.
The electrons are all paired as CN- is a strong field ligand.
Therefore, no d-d transition is possible in Ni(CN)4]2−. Hence, it is
colourless.

9.21 [Fe(CN)6]4- and [Fe(H2O)6]2+ are of different colours in dilute

solutions. Why?

38
In both the complexes Fe is in +2 oxidation state with the
configuration of 3d6.It has 4 unpaired electrons. Must draw the
Crystal field splitting diagram.

In the presence of weak H2O ligand, ∆o < P ,the electrons do not

pair up. d6 → t2g4, eg2
Where as in the presence of strong ligand CN-, ∆o > P ,
the electrons pair up d6 → t2g6, eg0 leaving no unpaired electron.
Due to the difference in the no. of unpaired electrons, they will
absorb different amount of energy from the visible spectrum and
undergo different types of d-d transitions.
Thus they exhibit different colours.

9.22 Explain why the magnetic moment of [Fe(CN)6]3- is 1.74BM

and that of [Fe(H2O)6]3+ 5.92 BM .

Must draw the Crystal field splitting diagram and the configuration.

In [Fe(H2O)6]3+ involves sp3d2 hybridisation and has 5 unpaired

electrons t2g3, eg2 as water is a weak ligand. Therefore Magnetic
moment 𝜇 = √(5 (5+2) = √(35 = 5.92 BM.

Where as [Fe(CN)6]3- has d2sp3 hybridisation and has one

unpaired electron, t2g5, eg0 as CN- is a strong ligand. Therefore
𝜇 = √(1 (1+2)= √3 = 1.73BM

Using Crystal field theory, draw energy level diagram , write

electronic configuration of the central atom/ ion and
determine the magnetic moment value in the following
[Co(F6)]3-, Co(H2O)6]2+,[Co(CN)6]3-

Magnetic moment 𝜇 = √(n (n+2)

[CoF6]3-
Co3+= 3d6 the electronic configuration is t2g4, eg2 . the number of
unpaired electrons, n= 4
Magnetic moment 𝜇 =√(4x 6) = 4.9BM

39
[Co(H2O)6]2+
Co2+ = 3d7. The electronic configuration is t2g5eg2
The number of unpaired electrons= 3
Magnetic moment = √(3 x 5) =3.87BM

[Co(CN)6]3-
Co3+ = 3d6 . The electronic configuration is t2g6 eg0

No unpaired electron, so it is diamagnetic.

9.23 Give the oxidation state, d-orbital occupation, and co-

ordination no of the central metal ion in the following
complexes.
1)K3[Co(C2O4)3, 2)cis-[Cr(en)2Cl2]Cl
3) (NH4)2[CoF4] 4) [Mn(H2O)6]SO4

complex O.state C.N d-orbital conf. No.of

unpaired
es
K3[Co(C2O4)3] +3 6 Co3+ =t2g6,eg0 0

cis- +3 6 Cr3+= t2g3 eg0 3

[Cr(en)2Cl2]Cl

(NH4)2[CoF4] +2 4 Co2+ =e4 , t23 3

[Mn(H2O)6]SO4 +2 6 Mn2+ = t2g3,eg2 5

9.32 What will be the correct order of the wavelengths of

absorption in the visible region for the following.
a) [Ni(NO2)6]4-,
b) [Ni(NH3)6]2+
c) [Ni(H2O)6]2-
The increasing order of field strength of the ligands is H2O < NH3 <
NO2-

40
The increasing order of energy absorbed be [Ni(H2O)6]2- < [Ni(NH3)6]2+
< [Ni(NO2)6]4-
As the wavelength is inversely proportional to the amount of
energy, increasing order of wavelength will be [Ni(NO2)6]4- <
[Ni(NH3)6]2+ < [Ni(H2O)6]2-

LIMITATIONS OF CRYSTAL FIELD THEORY

CFT is successful in explaining the formation of structures, colour

and magnetic properties of co- ordination compounds to a large
extent.

Its limitations are :

1. As ligands are considered as point charges, the anionic ligand

should exert the greater splitting effect. But these anionic
ligands are found at the low end of the spectro chemical
series.

2. It treats the metal-ligand bond as purely ionic and does not

account the co- valent character of the bond.

Bonding in Metal carbonyls

• Metal carbonyls of transition elements constitute an important

class of organometallic compounds.
• All d- block elements which contain only carbonyl ligands are
called homoleptic carbonyls.
• These carbonyls have well defined structures.
• [Ni(CO)4] is tetrahedral, [Fe(CO)5 is trigonal bi pyramidal,
[Cr(CO)6 is octahedral.
41
 • The metal carbon – metal bond in carbonyls possess both
sigma and pi character.
• The M-C sigma bond is formed by the donation of lone pair of
electrons on the carbonyl carbon into a vacant d- orbital of the
metal.
• The M-C pi bond is formed by the back donation of a pair of
electrons from a filled d-orbital of metal into the vacant anti
bonding 𝜋* orbital of carbon monoxide. (dπ−pπ back bonding)
As a result the bond between the metal and CO is
strengthened. This combined effect of sigma and the back pi
bond is called synergic effect.

• Structures of some homoleptic Carbonyls

Stepwise stability constant and overall stability constant of a

complex:
Complexes are formed from aqueous solutions and the reaction
involves the replacement of water molecules by the ligands in
various steps, each step is having its own formation constant.

[Cu(H2O)4]SO4 + 4NH3 ⇌ [Cu(NH3)4]SO4 + 4H2O

[Cu(NH3)4]SO4
K= [Cu(H2O)4]SO4 x [NH3]4

In step 1: [Cu(H2O)4]SO4 + NH3 ⇌ [Cu(NH3)(H2O)3]SO4 + H2O , k1

42
In step 2: [Cu(NH3)(H2O)3]SO4 + NH3 ⇌ [Cu(H2O)2 (NH3)2]SO4 + H2O, k2

In step 3: [Cu(H2O)2 (NH3)2]SO4 + NH3 ⇌ [Cu(H2O) (NH3)3]SO4 + H2O, k3

In step 4:[ [Cu(H2O) (NH3)3]SO4 + NH3 ⇌ [Cu(NH3)4]SO4 + H2O, k4

Where K, overall stability constant and k1 x k2 x k3 x k4 are and stepwise

stability constants.

The relation between stepwise stability constant and overall stability constant
is
K = k1 x k2 x k3 x k4

The factors on which stability of the complex depends :

(i) Charge on the central metal atom As the magnitude of charge
on metal atom increases, stability of the complex increases.

(ii)Nature of metal ion: Smaller the cation, and greater the charge
on it, more stable will be the complex.

(iii)Basic nature of ligands Strong field ligands form stable

complex. As the basic character of the ligand increases, stronger
the ligand

iv) the chelating ligands form more stable complex than

monodentate ligands.

pg no 266
9.31. Among the following the most stable complex is

1. [Fe(H2O)6]3+ ii)[Fe(NH3)6]3+
iiii) [Fe(C2O4)3]3- iv) [Fe(Cl)6]3-
In all these complexes Fe is in +3 oxidation state. As oxalate ion is
a didentate chelating ligand it forms a most stable ringed complex.

IMPORTANCE OF CO-ORDINATION COMPOUNDS:

43
 1. Hemoglobin is the complex of ‘Fe’ used as oxygen carrier
in the blood.
2. Chlorophyll is the Magnesium complex which is
responsible for photosynthesis.
3. Vitamin B12 is the complex of cobalt.
4. Complexes are used in photography. AgBr form complex
with sodium thiosulphate in photography
5. EDTA is used in estimation of Ca2+ and Mg2+ ions in water.
6. Silver and gold are extracted by treating Zinc with their
cyanide complexes.
7. Ni2+ is tested and estimated by DMG( Dimethyl glyoxime)

Uses in details: Analytical chemistry;

Co-ordination compounds find use in many qualitative and
quantitative chemical analysis.
In Qualitative analysis, in salt analysis the presence of a
number of basic radicals is confirmed by converting them into
suitable complexes which have definite colours.

1. Ni2+ is tested and estimated by treating salt solution with

dimethyl glyoxime in the presence of NH4OH which forms a
brilliant red ppt. of Nickel dimethyl glyoxime complex.
NiCl2 + 2DMG + 2NH4OH → [Ni(DMG)2] + 2NH4Cl + 2H2O

2. Cu2+ is detected based on the formation of a blue

tetraammine copper (11) ion complex
Cu2+ + 4NH3 → [Cu(NH3)4]2+

3.Confirmation of chloride radical with AgNO3 solution in

NH4OH
AgCl + 2NH3(aq) → [Ag(NH3)2]Cl

In Quantitative analysis: The amount of a metal present in a

given sample can be estimated by converting a known amount
of the sample into an insoluble complex which can be filtered
dried and weighed.
• The amount of nickel present in a salt is estimated by
precipitating it as Nickel dimethyl glyoxime complex.
44
 • EDTA can be used to estimate the hardness of water. The
hardness of water is estimated by simple titration with
Na2EDTA. The Ca2+ and Mg2+ form stable complexes with
EDTA. The selective estimation of these ions can be done
due to the difference in the stability constants of Calcium
and Magnesium complexes.
2. In metallurgy
The noble metals like Au, Ag are extracted from their ores
through the formation of cyanide complex. [Au(CN)2]- and
[Ag(CN)2]- by dissolving the ore in KCN and NaCN respectively.
The metal can be precipitated out from the complex by adding a
more electropositive metal like Zinc.
Ag2S + 4NaCN →2Na[Ag(CN)2] + Na2S
sodium dicyano argentite(1)
Na[Ag(CN)2] + Zn → Na2[Zn(CN)4 + 2Ag
Sodium tetra cyano zincate(11)

4Au + 8KCN + 2H2O + [O] → 4K[Au(CN)2] + 4KOH

2K[Au(CN)2] + Zn → K2[Zn(CN)4] + Au

3. IN PURIFICATION OF METALS
Mond’s Process: Metals like Nickel can be purified by converting it
into Nickel tetra carbonyl [Ni(CO)4] which on decomposition gives
pure metal.

Ni + 4CO → [Ni(CO)4]
[Ni(CO)4] → Ni + 4[CO]
Pure nickel
4. In Biological systems:
Chlorophyll,
Hemoglobin,
Cobalt complex- Cyano cobalamine Vitamine B12
Enzyme—Carboxy peptidase.

5. IN INDUSTRY USED AS
a) CATALYST Wilkinson’s catalyst used in selective
hydrogenation of alkene is a Co- ordination compound of
Rhodium. [{Ph3P}3RhCl] or
[RhCl(Ph3P)3]

45
 [ChloridotristriphenylphosphineRhodium(1).

b) In electroplating : Articles can be electroplated with Silver and

gold much more smoothly and evenly from solutions of the
complex [Ag(CN)2]- and [Au(CN)2]- than from solutions of
simple metal ions.
c) In Photography: In Black and white photography, the
developed film is fixed by washing with hypo solution which
dissolves the undecomposed AgBr to form a complex ion
[Ag(S2O3)]3-
AgBr + 2 Na2S2O3→ Na3[Ag(S2O3)2] + 2NaBr
Sodium dithiosulphatoargentate(1)
6. In Medical field:
a) EDTA is quite often used in treatment of lead poisoning.
Metals present in toxic proportions in animals and plants are
removed by chelate therapy. Excess of copper and iron are removed
by using chelating ligands D-Pencillamine and Desferrioxime B
through the formation of Co- ordination compounds.

b) CISPLATIN, Cis[Pt(NH3)2Cl2] a Platinum complex is useful in

the treatment of cancer(Tumers)

46