SRI KRISH INTERNATIONAL SCHOOL

A PROJECT REPORT ON

BONDING IN COORDINTION COMPOUNDS

SUBMITTED FOR SSCE

CHEMISTRY

SUBMITTED BY
R. TANUSHREE
XII B2 - SCIENCE STREAM

BONAFIDE CERTIFICATE

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This is to certify that TANUSHREE.R ,a student of GRADE XII
has completed chemistry project, entitled
‘BONDING IN COORDINTION COMPOUNDS’ under the guidance
of Mrs. T.KOWSALYA.,(PGT-CHEMISTRY) during the
academic year2024-25 in partial fulfillment of CHEMISTRY
PRACTICAL EXAMINATION conducted by SSCE, New
Delhi.

REGISTER NUMBER:

DATE OF EXAMINATION:

BIBILIOGRAPHY
 NCERT CHEMISTRY PART I

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 https://unacademy.com/content/cbse-class-12/study
material/chemistry/coordination-compounds/

 https://ncert.nic.in/textbook/pdf/lech109.pdf

 https://byjus.com/jee/coordination-compounds/

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 ACKNOWLEDGEMENT

I express my sincere gratitude to

Mr.Dr.R.KRISHNAMOORTHY
Chairman SRI KRISH INTERNATIONAL SCHOOL for
providing me with all the facility that was required to
complete my
project.

I am highly thankful to Mrs Dr. S. UDAYA CHITRA ,

principal for her valuable guidance and for her constant
encouragement.

I am highly thankful to Mrs. T. KOWSALYA DEVI.,(PGT-

CHEMISTRY) for her valuable guidance,support and for
her constant encouragement through out the duration of
the project. Without her motivation and help, the
successful completion of this
project would not have been possible.

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I am highly thankful to Mr MANOHAR T, lab incharge
for his valuable guidance and for his constant
encouragement.

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 TABLE OF CONTENTS
I. INTRODUCTION

II. WERNER’S THEORY

III. BONDING – VBT AND CFT

IV. NOMECLATURE OF COORDINATION

COMPOUNDS

V. DIFFERENCE BETWEEN DOUBLE SALT

AND A COMPLEX

VI. DEFINITION OF SOME INPORTANT

TERMS PERTAINING TO COORDINATION
COMPOUNDS

VII. ISOMERISM IN COORDINATION

COMPOUNDS

VIII. BONDING IN METAL CARBONYLS

IX. IMPORTANCE AND APPLICATION OF

COORDINATION COMPOUNDS

X. BIBLIOGRAPHY

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 INTRODUCTION

The Transition metals form a large number of

complex compounds in which the metal atoms
are bound to a number of anions or neutral
molecules. In modern terminology such
compounds are called as Coordination
Compounds. Chlorophyll, haemoglobin are
coordination compounds of magnesium and
iron. Variety of metallurgical process, industrial
catalysts and analytical reagents involve the
use of coordination compounds. Coordination
compounds also find many application in textile
dyeing, electroplating, and medicinal chemistry.

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 WERNER’S THEORY

Alfred Werner, a swiss chemist was the first to

formulate his ideas about the structures of
coordination compounds. Werner proposed the
concept of a primary valence and a secondary
valence. The main postulates are:
 In coordination compounds metals show two
types of linkages(valences)-primary and
secondary
 The primary valences are normally ionisable
and are satisfied by negative ions
 The secondary valences are non-ionisable.
These are satisfied by neutral molecules or
negative ions. The secondary valence is
equal to the coordination number and is
fixed for a metal
 The ions/groups bound by the secondary
linkages to the metal have characteristic
spatial arrangements corresponding to
different coordination numbers.


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 BONDING IN COORDINATION
COMPOUNDS

Werner’s theory was the first practical attempt

to define the nature of bonding in coordination
compounds, and it remains the most widely
accepted today. However, the Valence Bond
Hypothesis, introduced by Linus Pauling in 1931
and is the most straightforward theory that
explains the nature of bonding inside the
coordination sphere, is the most
straightforward.

I. VALENCE BOND THEORY: According to this

theory, the metal atom or ion under the
influence of ligands can use its(n-1)d, ns, np or
ns, np, nd orbitals for hybridisation to yield a set
of equivalent orbitals of definite geometry such
as octahedral, tetrahedral, square planar and so
on. These hybridisation orbitals are allowed to
overlap with ligand orbitals that can denote
electron pairs for bonding.

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Coordination compound bonding is presently
the subject of a slew of hypotheses. American
physicists Linus Pauling and John C. Slater
devised an important component of the valence
bond theory for coordination compounds, which
explains bonding by examining how many
empty electrons the metal ion’s hybridised
orbitals have. A coordinate-covalent bond is
formed when an unfilled metal ion orbital and a
filled ligand orbital overlap, and each ligand
provides an electron pair to do so.
As an example, sp (linear), sp3 (tetrahedron),
dsp2 (planar), and D2sp33 (octahedron) are all
examples of hybridizations in which orbitals of a
given type and number participate in the
hybridization. In many cases, the number of

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unpaired electrons measured is in agreement
with the theoretical forecast. By differentiating
between inner orbital complexes (d2sp3) and
outer orbital complexes (sp3d3), Henry Taube, a
Canadian-born American Chemistry Nobel
winner, further developed the theory in 1952 to
account for discrepancies between octahedral
complexes.
LIMITATIONS OF VALENCE BOND THEORY

It was unable to explain the precise magnetic

characteristics of the compounds in detail.

It could not provide an adequate explanation for

creating low spin and high spin complexes.

It does not provide a precise explanation for the

stability of coordination molecules in this
context.

It makes no distinction between ligands with a

weak field and those with a strong field.

In terms of the colour of the complexes, there is

no explanation given in the text.

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II. CRYSTAL FIELD THEORY: The Crystal Field
Theory (CFT) is a model for transition metal and
ligand binding interactions. It depicts the impact
of the ligand’s non-bonding electrons being
attracted by the positive charge of the metal
cation and the negative charge of the metal
cation. Due to the static electric field produced
by a surrounding charge distribution, the
degeneracy of electronic orbital states,
commonly d or f orbitals, is broken as the
ligands approach the core metal ion. CFT can
account for various magnetic characteristics,
hues, and hydration energies of transition metal
complexes, but it fails to account for bonding.

Due to repulsion between like charges, the

electrons in the d orbitals of the core metal ion
and those in the ligand repel each other. As a
result, the d electrons closest to the ligands will
have enormous energy than those further away,
dividing the energy of the d orbitals. This
division is influenced by:

 The metal ion’s composition.

 The oxidation state of the metal (a

higher oxidation state leads to a more
extensive splitting).

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 The ligands’ arrangement around the
metal ion.

 The ligands that surround the metal ion’s

nature.

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III. LIGAND FIELD THEORY: Ligand field
theory is the most powerful bonding theory for
coordination compounds. It is essentially
molecular orbital theory applied to coordination
compounds. It can explain covalent bonding in
coordination compounds, it can explain their
shapes, it can explain their magnetism, and
their electronic spectra. It can also explain the
stability of coordination compounds, in
particular the 18e rule and their exceptions. It
is, however, more complicated than other
bonding theories.
Just like in molecular orbital theory we can
apply symmetry adapted linear combination of
atomic orbitals to construct molecular orbitals.
However, slightly modified rules apply to
optimize molecular orbital theory for
coordination compounds. These modifications
are useful due to the greater complexity of
coordination compounds. In the first step we
determine the point group of the molecule and
assign axes in a useful way. In the second step,
we determine the valence orbitals, also called
frontier orbitals of the metal. For example, for a
transition metal of the 4th period we would
consider the 4s, the 4p, and the 3d orbitals as
the frontier orbitals. Next, we determine the
symmetry of these orbitals. We can do this by

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just looking into the character table of the
respective point group. In the following we
select the highest-energy ligand orbitals that
are suitable for σ-bonding. For ligands that are
molecules or polyatomic ions, these orbitals are
the HOMOs suitable for σ-bonding. For simple
ions like chloro-ligands these are the highest
occupied atomic orbitals. Next, we group the
selected ligand orbitals to form ligand group
orbitals (LGOs), and determine their symmetry
types. To do so, we determine the reducible
representation, and then the irreducible
representations of the LGOs. This gives us the
symmetry types of the ligand group orbitals. We
then combine metal frontier orbitals and ligand
group orbitals of the same symmetry type to
form molecular orbitals. Now we have
constructed all molecular orbitals suitable for σ-
bonding, and can draw a molecular orbital
diagram for the σ-bonding in the coordination
compound.
Next, we look for ligand orbitals that are
suitable for π-bonding with the metal. We then
determine the symmetry types of their ligand
group orbitals. Ligand group orbitals and metal
orbitals of the same symmetry will then be
combined to form molecular orbitals. These
MOs represent the π-bonding in the molecule.
We add these molecular orbitals to the
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molecular orbital diagram. Finally, we check if
there are ligand orbitals suitable for δ𝛿-bonding
with the metal. If so, we also form ligands group
orbitals for these, determine their symmetry
types, and combine ligand group orbitals and
metal orbitals of the same symmetry to form
molecular orbitals. These orbitals will then also
be added to the molecular orbital diagram.

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 NOMENCLATURE IN COORDINATION
COMPOUNDS
Nomenclature is important in coordination
chemistry because of the need to have
unambiguous method of describing formulas
and writing systematic names, particularly
when dealing with isomers

I. FORMULAS OF MONONUCLEAR
COORDINATION ENTITIES: Mononuclear
coordination entities contain a single central metal
atom. The following rules are applied while writing
the formulas:
 The central atom is listed first
 The ligands are then listed in alphabetical order.
The placement of a ligand in the list does not
depend on its charge.
 Polydentate ligands are also listed alphabetically.
In case of abbreviated ligand, the first letter of
the abbreviation is used to determine the
position of the ligand in the alphabetical order
 The formula for the entire coordination entity,
whether charged or not, is enclosed in square
brackets. When ligands are polyatomic, their
formulas are enclosed in parentheses. Ligand
abbreviations are also enclosed in parentheses
 There should be no space between the ligands
and the metal within a coordination sphere
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  When the formula of a charged coordination
entity is to be written without that of the counter
icon, the charge is indicated outside the square
brackets as a right superscript with the number
before the sigh.
 The charge of the cation is balanced by the
charge of the anion.

II. NAMING OF MONONUCLEAR

COORDINATION COMPOUNDS: They are
listed as prefixes to the name of the central
atom along with any appropriate multipliers. The
following rules are used when naming
coordination compounds:

(i) The cation is named first in both positively and

negatively charged coordination entities.
(ii) The ligands are named in an alphabetical order
before the name of the central atom/ion. (This
procedure is reversed from writing formula).
(iii) Oxidation state of the metal in cation, anion or
neutral coordination entity is indicated by Roman
numeral in parenthesis.
(iv) If the complex ion is a cation, the metal is named
same as the element. For example, Co in a complex
cation is called cobalt and Pt is called platinum. If the
complex ion is an anion, the name of the metal ends
with the suffix – ate is called cobaltate. For some

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metals, the Latin names are used in the complex
anions, e.g., ferrate for Fe.
(v) The neutral complex molecule is named similar to
that of the complex cation

DIFFERENCE BETWEEN DOUBLE

SALT AND A COMPLEX

Both double salts as well as complexes are formed by

the combination of two or more stable compounds in
stoichiometric ratio. However, they differ in the fact
that double salts such as carnallite, KCl.MgCl 2.6H2O,
Mohr’s salt, FeSO4.(NH4)2SO4.6H2O, potash alum,
KAl(SO4)2.12H2O, etc. dissociate into simple ions
completely when dissolved in water. However,
complex ions such as [Fe(CN)6]4- of K4[Fe(CN)6] do not
dissociate into Fe2+ and CN- ions

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 DEFINITIONS OF SOME IMPORTANT
TERMS PERTAINING TO COORDINATION
COMPOUNDS

(a) Coordination entity: A coordination entity

constitutes a central metal atom or ion bonded to a
fixed number of ions or molecules. For example,
[CoCl3(NH3 )3] is a coordination entity in which the
cobalt ion is surrounded by three ammonia molecules
and three chloride ions. Other examples are
[Ni(CO)4],[PtCl2 (NH3)2], [Fe(CN)6]4–, [Co(NH3)6] 3+ .
(b) Central atom/ion: In a coordination entity, the
atom/ion to which a fixed number of ions/groups are
bound in a definite geometrical arrangement around
it, is called the central atom or ion. For example, the
central atom/ion in the coordination entities:
[NiCl2(H2O)4], [CoCl(NH3)5]2+ and [Fe(CN)6]3– are Ni2+,
Co3+ and Fe3+, respectively. These central atoms/ions
are also referred to as Lewis acids.
(c) Ligands: The ions or molecules bound to the
central atom/ion in the coordination entity are called
ligands. These may be simple ions such as Cl -, small
molecules such as H2O or NH3, larger molecules such
as H2NCH2CH2NH2 N(CH2CH2NH2)3 or even
macromolecules, such as proteins.
When a ligand is bound to a metal ion through a
single donor atom, as with Cl –, H2O or NH3, the ligand

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is said to be unidentate. When a ligand can bind
through two donor atoms as in H 2NCH2CH2NH2
(ethane-1,2-diamine) or C2O42– (oxalate), the ligand is
said to be didentate and when several donor atoms
are present in a single ligand as in N(CH 2CH2NH2)3,
the ligand is said to be polydentate.
Ethylenediaminetetraacetate ion (EDTA4–) is an
important hexadentate ligand. It can bind through
two nitrogen and four oxygen atoms to a central
metal ion.
(d) Coordination number: The coordination number
(CN) of a metal ion in a complex can be defined as
the number of ligand donor atoms to which the metal
is directly bonded. For example, in the complex ions,
[PtCl6]2– and [Ni(NH3)4]2+, the coordination number of
Pt and Ni are 6 and 4 respectively. Similarly, in the
complex ions, [Fe(C2O4)3]3– and [Co(en)3]3+, the
coordination number of both, Fe and Co, is 6 because
C2O42– and en (ethane-1,2-diamine) are didentate
ligands
It is important to note here that coordination number
of the central atom/ion is determined only by the
number of sigma bonds formed by the ligand with the
central atom/ion. Pi bonds, if formed between the
ligand and the central atom/ion, are not counted for
this purpose.
(e) Coordination sphere: The central atom/ion and
the ligands attached to it are enclosed in square
bracket and is collectively termed as the coordination

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sphere. The ionisable groups are written outside the
bracket and are called counter ions. For example, in
the complex K4[Fe(CN)6 ], the coordination sphere is
[Fe(CN)6 ]4– and the counter ion is K+ .
(f) Coordination polyhedron: The spatial arrangement
of the ligand atoms which are directly attached to the
central atom/ion defines a coordination polyhedron
about the central atom. The most common
coordination polyhedra are octahedral, square planar
and tetrahedral. For example, [Co(NH3 )6]3+ is
octahedral, [Ni(CO)4 ] is tetrahedral and [PtCl4 ]2– is
square planar. Fig. 5.1 shows the shapes of different
coordination polyhedral
(g) Oxidation number of central atom: The oxidation
number of the central atom in a complex is defined
as the charge it would carry if all the ligands are
removed along with the electron pairs that are
shared with the central atom. The oxidation number
is represented by a Roman numeral in parenthesis
following the name of the coordination entity. For
example, oxidation number of copper in [Cu(CN)4]3– is
+1 and it is written as Cu(I).
(h) Homoleptic and heteroleptic complexes:
Complexes in which a metal is bound to only one kind
of donor groups, e.g., [Co(NH3)6]3+, are known as
homoleptic. Complexes in which a metal is bound to
more than one kind of donor groups, e.g.,
[Co(NH3)4Cl2]+, are known as heteroleptic

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 ISOMERISM IN COORDINATION
COMPOUNDS

Isomers are two or more compounds that have the

same chemical formula but a different arrangement
of atoms. Because of the different arrangement of
atoms, they differ in one or more physical or
chemical properties. Two principal types of isomerism
are known among coordination compounds. Each of
which can be further subdivided:

STRUCTURAL ISOMERISM
Linkage isomerism: arises in a coordination
compound containing ambidentate ligand. A simple
example is provided by complexes containing the
thiocyanate ligand, NCS– , which may bind through

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the nitrogen to give M–NCS or through sulphur to
give M–SCN. Jørgensen discovered such behaviour in
the complex [Co(NH3)5 (NO2 )]Cl2 , which is obtained
as the red form, in which the nitrite ligand is bound
through oxygen (–ONO), and as the yellow form, in
which the nitrite ligand is bound through nitrogen (–
NO2 ).
COORDINATION ISOMERISM: This type of isomerism
arises from the interchange of ligands between
cationic and anionic entities of different metal ions
present in a complex. An example is provided by
[Co(NH3 )6 ][Cr(CN)6 ], in which the NH 3 ligands are
bound to Co3+ and the CN– ligands to Cr 3+. In its
coordination isomer [Cr(NH3 )6 ][Co(CN)6 ], the NH3
ligands are bound to Cr3+ and the CN– ligands to
Co3+.
IONISATION ISOMERISM: This form of isomerism
arises when the counter ion in a complex salt is itself
a potential ligand and can displace a ligand which
can then become the counter ion. An example is
provided by the ionisation isomers [Co(NH 3 )5

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(SO4 )]Br and [Co( .

SOLVATE ISOMERISM: This form of isomerism is

known as ‘hydrate isomerism’ in case where water is
involved as a solvent. This is similar to ionisation
isomerism. Solvate isomers differ by whether or not a
solvent molecule is directly bonded to the metal ion
or merely present as free solvent moleculesin the
crystal lattice. An example is provided by the aqua
complex [Cr(H2O)6]Cl3 (violet) and its solvate isomer
[Cr(H2O)5Cl]Cl2 .H2O (grey-green)

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 STEREOISOMERISM
Stereoisomers have the same chemical formula and
chemical bonds but they have different spatial
arrangement. Structural isomers have different
bonds. A detailed account of these isomers are given
below:

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GEOMETRIC ISOMERISM: This type of isomerism
arises in heteroleptic complexes due to different
possible geometric arrangements of the ligands. The
two ligands X may be arranged adjacent to each
other in a cis isomer, or opposite to each other in a
trans isomer.

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IMPORTANCE AND APPLICATIONS
 Coordination compounds find use in many
qualitative and quantitative chemical analysis.
The familiar colour reactions given by metal ions
with a number of ligands (especially chelating
ligands), as a result of formation of coordination
entities, form the basis for their detection and
estimation by classical and instrumental methods
of analysis. Examples of such reagents include
EDTA, DMG (dimethylglyoxime), a–nitroso–b–
naphthol, cupron, etc.
 Hardness of water is estimated by simple
titration with Na2EDTA. The Ca2+ and Mg2+ ions
form stable complexes with EDTA. The selective
estimation of these ions can be done due to
difference in the stability constants of calcium
and magnesium complexes.
 Some important extraction processes of metals,
like those of silver and gold, make use of
complex formation. Gold, for example, combines
with cyanide in the presence of oxygen and water
to form the coordination entity [Au(CN)2]– in
aqueous solution. Gold can be separated in
metallic form from this solution by the addition of
zinc.
 Similarly, purification of metals can be achieved
through formation and subsequent
decomposition of their coordination compounds.
For example, impure nickel is converted to

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 [Ni(CO)4 ], which is decomposed to yield pure
nickel
 Articles can be electroplated with silver and gold
much more smoothly and evenly from solutions
of the complexes, [Ag(CN)2]– and [Au(CN)2]– than
from a solution of simple metal ions.
 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 )2]3–
 There is growing interest in the use of chelate
therapy in medicinal chemistry. An example is
the treatment of problems caused by the
presence of metals in toxic proportions in
plant/animal systems. Thus, excess of copper and
iron are removed by the chelating ligands D–
penicillamine and desferrioxime B via the
formation of coordination compounds. EDTA is
used in the treatment of lead poisoning. Some
coordination compounds of platinum effectively
inhibit the growth of tumours. Examples are: cis–
platin and related compounds.

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