Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

Introduction to Coordination Chemistry

S.Y. B. Sc. Sem-I, According to Revised Syllabus of SPPU - 2020
Prepared by

D. R. Shinde

Department of Chemistry
P. D. E. A’s. Prof Ramkrishna More College, Akurdi, Pune 411044

1. Double Salt and Coordination Compounds

Double salt is a stoichiometric mixture of two compounds. For example - Potash alum:
K2SO4∙Al2(SO4)3∙24H2O. It is the mixture of hydrated salts of K2SO4 and Al2(SO4)3. Another
example is - 4KCN∙Fe(CN)2. The basic difference is observed in these two compounds is that
the water solutions of show different characteristics. The aqueous solution of potash alum
shows the qualitative tests of K+, Al3+ and SO42- while aqueous solution of 4KCN∙Fe(CN)2 do
not shows the qualitative tests of CN- and Fe2+. Usually salts dissolve in water with dissociate
process to produce ions.
𝐻2𝑂
K2SO4∙Al2(SO4)3∙24H2O 𝑑𝑖𝑠𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛→ 2K+(aq) + 2Al3+(aq) + SO42-(aq)

Thus, ions of salt have individual existence in solution. Hence, they can be detected by
qualitative tests. In this regard potash alum show qualitative tests of K+, Al3+ and SO42- but
4KCN∙Fe(CN)2 gives positive test of K+ but not of Fe2+ and CN-. It means that these two ions
do have individual existence in solution. Thus, 4KCN∙Fe(CN)2 though dissolve in water it do
not dissociate completely to form ions. The solution show existence of K+ but not of CN-. It
means that K+ must not be associated with CN-. After rigorous study, scientists concluded that
4KCN∙Fe(CN)2 is not simple type of double salt but it is different type of chemical species.
The formula of this species could be written as K4[Fe(CN)6]. On dissolution it aqueous solution
it will produce 4K+ and [Fe(CN)6]4- ion. Thus, it can show the presence of K+ ions but not of
Fe2+ and CN- ions. Such double salts are termed as coordination complexes. Scientist Alfred
Werner was studied such many complexes and predicted basic theory of Coordination
complexes. For his work on coordination complexes he was honoured with Noble Prize in
1913.

At one night in late 1892, at the age of 26, Alfred Werner was awakened from his
sleep at two in the morning. He had just a dream about the nature of bonding in
coordination compounds. For the next 15 h, he recorded his insights that what
eventually he is thinking and published a paper. Before Werner, synthetic chemist
Jørgensen proposed the structures of Co(III) complexes very differently as follows.
These structures were well accepted at that and nobody was accepted the Werner’s
work. Jørgensen defeated Werner till 1907 and last accepted the Werners cocept.

1 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

2. Werner’s Work

After numerous works, in 1893 Werner's put his ideas regarding coordination
compounds called as Werner’s theory. It was the first successful attempt to explain the bonding
in coordination complexes and hence Werner is also called as Father of Coordination
Chemistry. He worked on salt CoCl3 and its reactions with ammonia. Werner observed that
under different reaction conditions, ammonia (NH3) react with CoCl3 and form series of
compounds which can be identified from their colours. He concluded that as colours of these
compounds are different, they must contain different quantity of NH3. Then he identified
composition of these complexes and really, he found difference in NH3 content. This is
depicted in table-1.

Table-1: Characteristics colours of the Compounds of CoCl3 with ammonia

Sr. No Composition of Colour No of ions by

Compound conductivity study
1 CoCl3∙3HN3 Violet 0
2 CoCl3∙4HN3 Green 2
3 CoCl3∙6HN3 Purple 3
4 CoCl3∙6HN3 Yellow 4

Afterwards, Werner studied conductivity of these substances. From conductivity study

in aqueous solution Werner obtained number of ions in these compounds which are as shown
in table-1. Observations are
i. In all four complexes there are three chloride ions but number ions in each compound are
different.
ii. Colour do not depend upon number of chloride ions but depends upon number of NH3 in the
compound.
iii. Conductance of each solution at same molar concentration is different.
Then with the help of simple experiment Werner obtained ionizable Cl- ions present in
each of these compounds. He titrated aqueous solution of these compounds with AgNO3 and
obtained moles of AgNO3 consumed per mole of substance. In this reaction only dissociated
Cl- ions react with AgNO3. The results of this experiment are shown in table-2. He observed
that in each compound ionizable Cl- ions are different. From this experiment observations are;

2 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

i. With increasing number of NH3 molecules in the compounds, the ionizable chloride
ion increases.
ii. The sum of ammonia and non-ionizable chlorides remains constant and it is 6.
iii. Number of ionizable and non-ionizable Cl- ions in compound depends upon number
of ammonia molecules in the compound.

Table-2: Characteristics of the Compounds of CoCl3 with ammonia

Reaction Moles of Dissociation Moles of AgNO3 No of Sum of NH3

AgCl reaction required and non- and non-
ionizable ionizable ionizable Cl-
formed Cl - ions Cl - ions Ions
CoCl3∙3HN3 + CoCl3∙3HN3 →
AgNO3
0AgCl (CoCl3∙3HN3)aq + 0Cl-
0 3 3+3=6
CoCl3∙4HN3 + CoCl3∙4HN3 →
AgNO3
1AgCl (CoCl2∙4HN3)aq + Cl-
1 2 4+2=6
CoCl3∙5HN3 + CoCl3∙5HN3 →
AgNO3
2AgCl (CoCl∙5HN3)aq + 2Cl-
2 1 5+1=6
CoCl3∙6HN3 + CoCl3∙6HN3 →
AgNO3
3AgCl (Co∙6HN3)aq + 3Cl-
3 0 6+0=6

Conclusions of the experiment are-

i. In these compounds, cobalt has +3 oxidation state, hence it requires 3Cl- ions for complete
neutralization of charge on Co(III) ion.
ii. Ionizable and non-ionizable chlorides are bonded differently to Co(III) ion.
iii. All NH3 molecules are bonded similarly to Co(III) ions.
To explain these conclusions, Werner proposed the concept of primary and secondary
valency in these compounds. This is nothing but Werner’s theory of coordination compounds.
i. Primary Valency: It is equal to the oxidation state of metal ion. It is satisfied by -vley
charged ion in coordination complex. It is not fixed i.e. variable. The -vely charged ions
completely neutralize the +ve charge of the metal ion.
ii. Secondary Valency: Secondary valency is the number of non-ionizable chemical species
(negative ion or neutral molecule or positive ions) associated with metal ion in coordination
complex. Secondary valency is fixed and it is nonionizable. For example, in CoCl3∙3HN3,
CoCl3∙4HN3, CoCl3∙5HN3, and CoCl3∙6HN3 secondary valency is 6.
iii. The secondary valency is equal to the coordination number of the metal ion.
iv. Negatively charged ions may satisfy primary as well as secondary valency of metal ion.
Example, in the complex CoCl3∙3HN3 i.e. [CoCl3(NH3)3], three Cl- are satisfying both
valencies of Co(III) ion. In this case, both NH3 and 3Cl- are non-ionizable. In the Complex
CoCl3∙6HN3 i.e. [Co(NH3)6]Cl3, six NH3 satisfy secondary valency while 3 Cl- ions satisfy
only primary valency. Thus, 6NH3 are non-ionizable while 3Cl- ions are ionizable. Thus, on
this basis, Werner proposed new scheme of writing formula of these coordination complexes
as follows:

3 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

Table-3: Writing formula of coordination complex

Sr. No Composition Writing Formula of

of Compound coordination complex
1 CoCl3∙3HN3 [Co(NH3)3Cl3]
2 CoCl3∙4HN3 [Co(NH3)3Cl2]Cl
3 CoCl3∙6HN3 [Co(NH3)3Cl]Cl2
4 CoCl3∙6HN3 [Co(NH3)6]Cl3

vi. Negative ions satisfying only primary valency are ionically bonded to the metal ion i.e.
associated with complex ion by electrostatic force of attraction.
vii. Ions Satisfying only primary valency dissociated in aqueous solution while ligands / ions
satisfying secondary do not dissociate in aqueous solution.
viii. Metal and ligand together form neutral or -vely charged or +vely charged species is called
as complex or complex ion. Example –[CoCl3(NH3)3], [CoCl2(NH3)4]+, [CoCl(NH3)5] 2+,
[Co(NH3)6]3+ represents the complex or complex ions.
ix. Secondary valency is directional i.e. the ligands are oriented at specific direction in the
space around the central metal ion. It means that complex or complex ion has definite
structure / geometry. This is shown in figure-1. The complex with coordination number six
has octahedral geometry.

Figure-1: Structure of [Co(NH3)4Cl2]Cl and [Co(NH3)6]Cl3 Complexes

How the structures are proved by Werner? The concept of isomerism is used by Werner
to predict possible structure of complex ion. For coordination number-6, three structures are
possible (figure-3). These are hexagonal, octahedral and trigonal prismatic.

Figure-3: Possible structures with coordination number six

Then depending on isomerism study structures were finalized. Practically, for the
complex [Co(NH3)4Cl2]+ only two isomers were isolated. Theoretically, for hexagonal and
4 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

prismatic structure three isomers are possible while for octahedral structure two isomers are
possible (figure-4). Therefore, Werner concluded that this compound should have octahedral
structure. Same is true for [Co(NH3)3Cl3] complex. Afterwords, this was found very correct
conclusion by Werner which was proved correct on the basis of structures obtained using
modern technique of X-ray crystallography.

Figure-4: Two possible isomers of each [Co(NH3)4Cl2]+ and [Co(NH3)3Cl3] complex ions

Similarly, Werner worked on isomerism and structure of four coordination complexes.

For four coordination number two structures are possible. a) tetrahedral and b) square planar.
He synthesized coordination complexes of Pt(II) i.e. Pt(NH3)2Cl2 with coordination number
four. With this formula he worked on isomerism and practically he was able to isolate only two
isomers. Theoretically, for i) tetrahedral structure only one isomer is possible for the formula
[Pt(NH3)2Cl2]. ii) square planar structure two isomers are possible (figure-5). Thus, Werner
concluded that ]Pt(NH3)2Cl2] must have square planar structure. Afterword’s, on the basis of
x-ray crystallography structure of Pt(NH3)2Cl2 was found correct.

Figure-5: Possible isomers of [Pt(NH3)2Cl2]

Importance of Werner’s Work: When Werner predicted his idea of bonding and
structure for coordination compounds, the idea was very new and at that time

5 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

leading scientist in chemistry do not accepted his idea nearly for 15 years. At
that time there is no idea of electronic structure of molecules and no advanced
technique in the hand of Werner and scientist. Werner did his research using
simple equipment’s conductometer and potentiometer and with the concept of
isomerism. Whatever he proposed in his theory was hold very true on the basis
of electronic structure of molecule. The proposed structures of coordination
compounds were proved highly accurate on the basis of X-ray crystallography.
Thus, without availability of advance equipment what Werner was achieved at
that time was amazing. His idea was found revolutionary in chemistry and
directly and indirectly contributed much more in the advancement of structure
and bonding in chemistry. Hence, he was honoured with Nobel prize.

3. Effective Atomic Numbers

Effective atomic number is used to explain secondary valency i.e. coordination number
of central metal ion. Ligand donates pair of electrons to the central metal ion. Thus, during
formation of bond between metal and ligand, central metal ion gains electrons. Sidgwick
observed that in many coordination complexes, number of coordinate bonds formed by central
metal ion depend upon number of electrons required by central metal ion to complete the inert
gas configuration. [Inert gas configuration is most stable electronic arrangement in atoms and
molecules]. Thus, Effective Atomic Number (EAN) is defined as, the metal ion form number
of coordinate bond with ligands so as to complete electronic configuration of inert gas
configuration. Or The metal ion form number of coordinate bond with ligands so as to have
18 electrons in its outermost shell of electron.
Examples: a) K4[Fe(CN)6]
i. Central metal ion = Fe(II), At No – 26, Electronic configuration, 4s0, 3d6
ii. Fe(II) has 6 electron in 3d orbital or 24 total electrons in ion.
iii. Each cyanide donate 2 electrons, therefore 6CN = 6×2 = 12 e-
iii. Total electrons in outer most shell of Fe(II) = 6 + 12 = 18 electron
iv. Alternatively, Fe(II), has 24 electrons, 6CN donate 12 e-. Therefore, total electrons
= 24+ 12 = 36 electron which is inert gas configuration (i.e. of Kr at no 36).
b) [Cr(CO)6]
i. Central metal ion = Cr, At No – 24, Electronic configuration, 4s1, 3d5
ii. Cr(0) has 6 electron in 3d orbital or 26 total electrons in metal.
iii. Each CO donate 2 electrons, therefore 6CO = 6×2 = 12 e-
iii. Total electrons in outer most shell of Cr(0) = 6 + 12 = 18 electron
iv. Alternatively, Cr(0), has 26 electrons, 6CO donate 12 e-. Therefore, total electrons
= 24+ 12 = 36 electron which is inert gas configuration (i.e. of Kr at no 36).

6 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

c) [Cu(CN)4]3-
i. Central metal ion = Cu(I), At No – 29, Electronic configuration, 4s0, 3d10
ii. Cu(II) has 10 electron in 3d orbital or 28 total electrons in ion.
iii. Each cyanide donate 2 electrons, therefore 4CN = 4×2 = 8 e-
iii. Total electrons in outer most shell of Cu(I) = 10 + 8 = 18 electron
iv. Alternatively, Cu(I), has 28 electrons, 4CN donate 18 e-. Therefore, total electrons
= 28+ 8 = 36 electron which is inert gas configuration (i.e. of Kr at no 36).
Many complexes do no obey EAN rule but are stable. Following are the exceptions
EAN Rule:
a) [Ni(CN)4]2-
i. Central metal ion = Ni(II), At No – 28, Electronic configuration, 4s0, 3d8
ii. Ni(II) has 8 electron in 3d orbital or 26 total electrons in ion.
iii. Each cyanide donate 2 electrons, therefore 4CN = 4×2 = 8 e-
iii. Total electrons in outer most shell of Ni(II) = 8 + 8 = 16 electron
iv. Alternatively, Ni(II), has 26 electrons, 4CN donate 8 e-. Therefore, total electrons
= 26 + 8 = 34 electron
b) K3[Fe(CN)6]
i. Central metal ion = Fe(III), At No – 25, Electronic configuration, 4s0, 3d5
ii. Fe(III) has 5 electron in 3d orbital or 25 total electrons in ion.
iii. Each cyanide donate 2 electrons, therefore 6CN = 6×2 = 12 e-
iii. Total electrons in outer most shell of Fe(III) = 5 + 12 = 17 electron
iv. Alternatively, Fe(III), has 25 electrons, 6CN donate 12 e-. Therefore, total electrons
= 25+ 12 = 35 electron.
Such many exceptions to EAN rule can be given. Particularly, if metal ion have odd
number of electrons then EAN rule cannot be obeyed. Though, in such complexes central metal
ion do not have inert gas configuration, they are stable. This indicate that inert gas configuration
is not necessary condition but have significant contribution in stability of complexes. The
symmetrical arrangement of ligands around central metal ion is much more important. In this
regard the important observation is that when ligand arrangement is symmetric around central
metal ion then complexes are stable. In each case Td, Oh, and Sq. Pl. ligand arrangement
around central metal ions has some kind of symmetry.

4. Basic Definition and Concepts in Coordination Chemistry

i. Ligand: Negative ion or neutral molecule or positive ions bonded to metal ion in
coordination complex by coordinate bond is called as ligand. Example: NH3, CN-, H2O, Cl-
, NO2-, etc. Ligand is electron rich species and donate a lone pair of electrons (non-bonded
electrons) to the metal ion. It is Lewis base.
7 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

ii. Coordinate Bond: The bond formed between metal and ligand where both electrons in a
bond are shared by ligand only. Coordinate bond is shown by single headed arrow pointing
from ligand towards the metal ion. L→M. (L – ligand, M-Metal). The ligand act as electron
pair donor to the metal ion while metal act as electron pair acceptor. Coordinate bond has
same properties as that of covalent bond, only the way of formation is different. Like
covalent bond, coordinate bond is also formed by orbital overlap where fulfilled orbital of
ligand overlaps with empty orbital of metal ion. Thus, it is normal type of covalent bond.
Thus, in aqueous solution the bond between metal and ligand do not dissociate as like that
of ionic bond. (Ionic bond is formed due to electrostatic force of attraction between cation
and anion hence it dissociates in aqueous solution).

iii) Complex ion: The neutral or -vely charged or +vely charged chemical species formed by
combination of metal ion and ligand is called as complex ion. Example: in K3[Fe(CN)6],
[Fe(CN)6]3- is complex ion. Likely in [Co(NH3)4Cl2]Cl, [Co(NH3)4Cl2]+ are complex ions.

iv) Central metal ion: In complex ion ligands are bonded to the metal ion by coordinate
bond, it is called as central metal ion. Example- In K3[Fe(CN)6], Fe(III) is central metal
ion, [Co(NH3)4Cl2]Cl, Co(III) is a central metal ion.

v) Charge on complex ion: Charge on complex ion is the algebraic sum of charge on central
metal ion and ligand. Ligands have fixed charges. Some of the ligand and their charges are
recorded in table-4. From charge on ligand and metal ion charge on complex ion can be
calculated (Table-5).
Table-4: Ligand and charges on the ligands

Ligand Charge
F-, Cl-, Br-, I-, OH-, CN- -1
C2O42-, SO42-, CO32- -2
H2O, Ethylene diamine (en), NH3, CO, 0
Acetyl acetone (acac)
Table-5: Calculation on charge on complex ion

Charge on Charge on
Complex ion Sum of charges of Ligand
metal ion complex ion
[Co(NH3)4Cl2]+ +3 (0×4) NH3+ (-1×2)Cl = -2 +3 – 2 = +1
[Fe(CN)6]3- +3 (-1×6) = -6 +3 – 6 = –3
[Fe(CN)6]2- +2 (-1×6) = -6 +3 – 6 = –4
[Cu(NH3)]2+ +2 (0×4) = 0 +2 – 0 = +2
vi) Calculation of oxidation state of metal ion:

Metal ion in coordination complex may have variable oxidation state, for example Fe
may have +2 or +3 oxidation state, Pt may have +2 or +4 oxidation state, Co may have +2
or +3 oxidation state, etc. From charge on complex ion and charge on ligand, oxidation state
of metal ion can be calculated. The rule is simple. Total charge on coordination complex is
the algebraic sum of charges of all ions in the coordination complex. Examples are as
follows:

8 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

a) K4[Fe(CN)6]
i. Central metal ion = Fex, x to be calculate (x is charge on central metal ion)
ii. Charge on each K is +1, therefore charges to 4K = +4
iii. Each cyanide has -1 charge, therefore charges to 6CN = -6
iv. Total charge = x+4-6 = 0, therefore X = +2
v. Therefore, oxidation state of metal ion is +2.
b) K3[Fe(CN)6]
i. Central metal ion = Fex, x to be calculate (x is charge on central metal ion)
ii. Charge on each K is +1, therefore charges to 3K = +3
iii. Each cyanide has -1 charge, therefore charges to 6CN = -6
iv. Total charge = x+3-6 = 0, therefore X = +3
v. Therefore, oxidation state of metal ion is +3.
c) [Co(NH3)6]Cl3
i. Central metal ion = Cox, x to be calculate (x is charge on central metal ion)
ii. Charge on each NH3 is 0, therefore charges to 6NH3 = 0
iii. Each chloride has -1 charge, therefore charges to 3Cl = -3
iv. Total charge = x+0-3 = 0, therefore X = +3
v. Therefore, oxidation state of metal ion is +3.
d) [Cu(NH3)4]2+
i. Central metal ion = Cux, x to be calculate (x is charge on central metal ion)
ii. Charge on each NH3 is 0, therefore charges to 4NH3 = 0
iii. Total charge = x+0 = +2, therefore x = +2
iv. Therefore, oxidation state of metal ion is +2.
e) [Ni(en)3]2+
i. Central metal ion = Nix, x to be calculate (x is charge on central metal ion)
ii. Charge on each en ligand is 0, therefore charges to 3en = 0
iii. Total charge = x+0 = +2, therefore x = +2
iv. Therefore, oxidation state of metal ion is +2.
f) [Ni(CN)4]2-
i. Central metal ion = Nix, x to be calculate (x is charge on central metal ion)
ii. Charge on each CN ligand is -1, therefore charges to 4 CN = - 4
iii. Total charge = x - 4 = -2, therefore x = +2

9 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

iv. Therefore, oxidation state of metal ion is +2.

vi) Types of ligands:

A ligand can form one or more bond with central metal ion. Depending on this ability of
ligand they classified as follows:
i. Monodante ligand: The ligand which form only one bond with metal ion is called as
monodante ligand. Examples - F-, Cl-, Br-, I-, OH-, CN-.
ii. Bidante ligand: The ligand which forms two bonds with metal ion is called as bidante
ligand. Examples - C2O42-, SO42-, CO32-, en, acac, bipyridyl, etc.
ii) Polydante ligands: They can form three or more bonds with metal ion. Polydante ligand
may be:
a. Tridante ligand: The ligand which forms three bonds with metal ion is called as
tridante ligand. Examples – diethyletriamine (diene).
b. Tetradante ligand: The ligand which forms four bonds with metal ion is called as
tetradante ligand. Examples – triethyletetramine (triene).
c. Pentadante ligand: The ligand which forms five bonds with metal ion is called as
pentadante ligand. Examples -tertaethylenepentamin ( etc.
d. Hexadante ligand: The ligand which forms six bonds with metal ion is called as
hexadante ligand. Examples – Ethylenediamine tetracetic acid (EDTA).

vii) Chelate: Consider the structure of [Cu(en)2]2+ complex ion. Each ethylene diamine
ligand form two bont with Cu(II) ion. Thus, including Cu(II) ion ligand form pentagonal
ring structure in the complex ion. Thus, the complex ion in which ligand form ring structure
with metal is called as chelate.

Figure-6: Structure of [Cu(en)2]2+

Chelated complex is more stable than the ligand containing monodante ligands only.
Since in chelated complex for dissociation of one ligand two or more bonds are required to be
broken rather one bond in monodante ligand. Thus, stability of chelate is more and it is even
more when it consists of a greater number of rings in it. All polydante ligands are chelating
ligands. Some of the chelate forming bidante ligands are shown in figure – 7.

10 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

44
Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

O
O- H3C
NH2 N
C C O
H2C
HC
C N
H2C C O
O O- NH2
H3C
Oxalato ligand Ethylediamine Acetyl acetone 1,10 phenolthrolein

C2H5 S O- N
N
-
N C O
C
C2H5 O N
S
O

Diethy ditiocarbamate 8 -hydroxyquinoline Salicylic acid bipyridyl

Figure-7: Structure of some important bi-dante ligands

Several metal-protein complexes (metalloenzymes) in biological systems are coordination

complexes containing chelate type of ligand. Such as haemoglobin. It is a Fe(II) containing
metal protein complex (it contain porphyrine ring structure and N donor atoms). Anoter
examples are chlorophyll - Mg(II) - porphyrine complex, vitamin B12 (cyanocobalmin) -
Co(III) containing complex. In the treatment of metal ion poisoning such as Pb(II) the chelating
ligand like EDTA is used as antidot. To avoid blood clotting, Na2EDTA is added in blood
sample where Ca(II)-EDTA chelate is formed. This complex avoid Ca(II) to take part in blood
coagulation thus, blood coagulation do not take place.

4. Nomenclature of Coordination Compounds:

The IUPAC nomenclature rules for coordination compounds are as follows:

1. The ionically bonded cation in coordination compound is listed first, then a space, followed
by the name of complex ion, than space, name of ionically bonded anion.
2. In naming complex ion, ligands are listed first, followed by the name of the metal with its
oxidation state in parentheses. This as a single word.
The names of some ligands are listed in table-6.
Table-5: names of some common ligands in naming coordination compound

Ligand Name Ligand Name

F- Fluoro NH2-CH2-CH2-NH2 (en) Ethylenediamine
Cl- Chloro CH3COCH2COCH3 (acac) Acttylacetone
Br- Bromo Oxalate – C2O42- Oxalato
I- Iodo Water – H2O aquo
OH- Hydroxo Ammonia -NH3 Amine
CN- Cyano Carbonate – CO32- Carbonato
SCN- Thicyano Carbon monoxide - CO Carbonyl
NCS- Isothicynato -NH2 Amido
NO2- Notrito S2O32- Thiosulfato
NO Nitrosyl SO42- Sulphato
H- Hydrido [EDTA]2- Ethylenediamine
tetraacetato

11 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

44
Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

3. The following prefixes are used to before the name of the ligands to indicate the number
of each type of ligand in the complex ion.
a. If the ligand is monodentate, the prefix are di for 2, tri for 3, tetra for 4, penta for 5, and
hexa for 6 ligands.
b. If the ligand is a chelate, the prefix are: bis for 2, tris for 3, tetrakis for 4, pentakis for 5,
hexakis for 6 ligands. In this case name of ligand is written in parenthesis.
4. Other prefixes, such as cis- and trans-, are used to designate geometrical or optical isomers,
whenever this is necessary.
5. If the ligand is a bridge between two metals, the symbol 𝜇- is used as a prefix before the
bridging ligand.
6. The ligands in complex ion are listed in alphabetical order of the ligand’s name (ignoring
any prefixes).
7. If the anion is a coordination compound, the suffix -ate is used; some metals have special
names in this case: ferrate (Fe), stannate (Sn), argentate (Ag), and aurate (Au)

Example

a. K4[Fe(CN)6] - Potassium hexacyanoferrate(II)

b. [Co(NH3)5Cl]Cl2 - Pentaamminechlorocobalt(III)

c. [Fe(acac)3] - tris(acetylacetato)iron(III)

d. [Pt(en)2Cl2]Cl2 - dichlorobis(ethylenediamine)platinum(IV) chloride

e. Na[PtBrCl(NO2)NH3] - Sodium amminebromochloronitritoplatinate(II)

f. [Co(NH3)6]Cl3 – Hexaaminecobalt(III) chloride

g. (NH3)5CoNH2Co(NH3)5](NO3)5 – μ amidobis[pentaaminecobalt(III)] nitrate

h. [(CO)3Fe(CO)3Fe(CO)3] – Tri μ carbonylbis(tricarbonyliron(0)

5. Stability constants
The thermodynamic stabilities of coordination compound is measured using stability
or formation constants. For a reaction-
M+L ML
The formation constant or equilibrium constant can be written as
[𝑀𝐿]
K = [𝑀][𝐿]
K – equilibrium constant or formation constant

[ML] – Concentration of complex formed under equilibrium condition,

[M] – unreacted metal ion conc. in complex solution

12 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-
44
Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

[L] - unreacted ligand conc. in complex solution

Now consider the Complex MLn where n is coordination number (it may 2 to 6
depending on metal ion. Ag(I) - 2, Pt(II) – 4 or 6, Co(III) – 6) and L is monodante ligand. You
can consider formation of complex in one step or as multistep reaction.
a) Multistep reaction – stepwise formation of complex MLn
[ML]
M+L ML step-1 K1 =
[M] [L] ----- 1

[ML2]
ML + L ML2 step-2 K2 = ----- 2
[ML] [L]
[ML3]
ML2 + L ML3 step-3 K3 = ----- 3
. . [ML2] [L]
. .
. .
[MLn]
MLn step- 4 Kn = ----- 4
MLn-1 + L [MLn-1] [L]

In this case formation constants are also written in stepwise manner through equation 1
to 4 and K1, K2 ----Kn represent the stepwise formation constants.
Another way of formation of MLn complex is to consider that reaction is taking in one
step as:
M + nL MLn
Formation constant can be written as in equation-5, where βn represents the overall
stability constants.
[MLn]
n = ----- 5
[M] [L]n

The relationship between stepwise and overall formation constant must be there as final
product in both the cases is same. Thus, we have equation 6 for this relationship.
i=k
n = K1 K2 K3 .....Kn = Ki ----- 6
i=1
The stepwise formation constant is important where product is less stable and value of
formation constant or stability constant is low. For such complexes the metal ligand ratio is
dependent upon ligand concentration. Example – Formation of [Cd(NH3)4]2+ complex.
Cd(II) + NH3 → [Cd(NH3)]+ K1 = 102.65
[Cd(NH3)]++ NH3 → [Cd(NH3)2] K2 = 102.10
[Cd(NH3)2]+ NH3 → [Cd(NH3)3]- K3 = 101.44
[Cd(NH3)3]-+ NH3 → [Cd(NH2)] 2- K4 = 100.93
β4 = 10[2.65+2.10+1.44+0.93) = 107.12

13 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

44
Organic Inorganic Chemistry Paper-II SPPU 2020 Revised Syllabus

In stepwise formation of complex first step is rapid and the complex formed is more
stable. Then in series, the formation of higher complexes take place by addition of one ligand
in one step and process is slow. With increasing number of ligand stability decreases and give
rise to less values of stability constant. For example in the formation of [Cd(NH3)4]2- the species
[Cd(NH3)3]- is used. When we increase concentration of NH3 we get formation of [Cd(NH3)4]2-
complex take place but at the same time more quantity of [Cd(NH3)3]- is also formed in the
solution. Thus, effect of increase in concentration of ligand is dual. It forms [Cd(NH3)4]2- as
well as increases the concentration of [Cd(NH3)3]- species. Thus, overall effect is decrease in
value of stability constant of [Cd(NH3)4]2- complex ion. From above example this well proven.
The steady decrease in equilibrium constant is observed as number of ligands increases. This
is obvious and natural.

14 | P a g e D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-

44