CBSE Class 12 Chemistry Chapter 9 Coordination Compounds Revision Notes

Bonding in Metal Carbonyls
What do you know about carbonyl ligands? Or is it the first time you
are actually coming across this term? Well, do not worry! We will
help you in that. In this chapter, we will look at the concept of
bonding in various metal carbonyls. However, before we proceed, let
us first look at what carbonyls are?
Brief about Metal Carbonyls
We are aware of many complex compounds having carbonyl ligands,

We call them homoleptic carbonyls. We can, otherwise, call them
metal carbonyls. So, which elements form these carbonyls? Maximum
of the transition metals specialise in forming homoleptic carbonyls or
metal carbonyls. These have simple and very well-defined structures.
For example, their structures are usually tetrahedral, octahedral etc.
In a metal carbonyl, the metal-carbon bond has the characteristics of

both σ and π bonds. The bond between the carbonyl molecule and the
metal becomes stronger by the synergic effect that the metal-ligand
bond produces. We will explain the two types of bonding in metal
carbonyls in the section below.
Structure of Metal Carbonyls
The formation of a metal-carbon σ bond takes place because of the

donation of electrons by the carbonyl molecules. To what do they
donate these electrons? They donate it to the vacant orbitals of the
metal. This is one way of formation of the metal carbonyls.
The other form is the creation of a metal-carbon π bond because of the

donation of a pair of electrons from a filled d orbital metal into the
vacant antibonding π* orbital of carbonyl ligand.
Stability of Carbonyl Compounds
How stable are these coordination compounds? Well, we have

practical evidence that suggests these compounds to break down or
dissociate in various solutions. The stability of a coordination
compound in a solution mainly depends on upon the degree of
association between the two species involved in the state of
equilibrium.
Quantitatively speaking, the stability of any complex is the magnitude

of the equilibrium constant for the formation of the compound. A
general example is given below:
A + 4B → AB4
In the above example, the amount of AB4 molecule in the solution

depends on upon the value of the equilibrium constant, k. This k is
also what we know as the stability constant. On the other hand, the
instability constant or the dissociation constant of complexes is
nothing but the reciprocal of the equilibrium constant of the formation
reaction.
Solved Example for You
Q: Write a note on the physical characteristics of carbonyl

compounds.
Ans:
● Most of these carbonyl compounds are colourless or pale
yellow in colour and are generally volatile in nature.
● We can find them as liquids or solids that are flammable and
toxic. For example, Vanadium hexacarbonyl, which is a stable
17-electron metal carbonyl, is a blue-black solid. It is a unique
compound. Di- and polymetallic carbonyls have deeper colours
as compared to the others. The crystalline metal carbonyls
usually undergo sublimation in the vacuum.
● Metal carbonyls are soluble in both non-polar and polar organic
solvents. These include benzene, diethyl ether, and carbon
tetrachloride. Some salts of metal carbonyls are soluble in
water or lower alcohols.
Crystal Field Theory
We have heard of the Valence bond theory, VSEPR theory and even
Werner’s theory. But what is the Crystal field theory? Sounds new?
Well, it will become familiar once you read this topic. We will cover
all of it. But first, we will start with what the theory is all about!
What is the Crystal Field Theory?
The valence bond theory could not explain the stability of the
coordination compounds. It also failed to throw a light on the
differences between strong and weak ligands. Therefore, scientists
proposed the crystal field theory.
According to this theory, the metal-ligand bond acts as an ionic bond

arising purely from the electrostatic interactions between the metal
ions and ligands. This theory takes anions as point charges and neutral
molecules as dipoles. When the transition metals do not bond to any
ligand, their d orbitals degenerate. This means that they have the same
amount of energy.
When they start bonding with other ligands, the d orbitals split apart
and become non-degenerate. This bonding occurs mainly due to
different symmetries of the d orbitals and the inductive effect of the
ligands on the electrons. The pattern of the splitting of d orbitals
depends on upon the nature of crystal field.
Splitting of Crystal Fields
In case of an octahedral coordination compound, there are six ligands

that surround the metal atom/ion. In these cases, we observe repulsion
between the electrons in d orbitals and ligand electrons. This repulsion
is more in the case of dx2-y2 and dz2 orbitals. This is because they point
towards the axes along the direction of ligand. Hence, their energy is
higher as compared to the average energy in spherical crystal field.
While, dxy, dyzand dxz orbitals experience lower repulsions as they are
directed between the axes. Hence, these three orbitals possess lower
energy than the average energy in spherical crystal field. Thus, we get
two energy levels:
● t2 g– set of three orbitals (dxy, dyz and dxz) with lower energy
● eg – set of two orbitals (dx2-y2 and dz2) with higher energy
Crystal Field Splitting
It is the process of the splitting of degenerate level in the presence of

ligand. The difference between the energy of t2g and eg level is
denoted by “Δo”. There are some ligands producing strong fields and
causing large crystal field splitting. On the other hand, others produce
very weak fields.
Thus, the crystal field splitting depends on upon the field produced by
the ligand and the charge on the metal ion. We can arrange ligands in
order of their field strength as:
I– < Br– < Cl– < SCN– < F– < OH– < C2O42-< H2O <NCS– < EDTA4- <
NH3 < en < CN–< CO
Q: How does the filling of d-orbitals take place, according to the

crystal field splitting theory?
Ans: Filling of d-orbitals takes place as follows:
The first three electrons arrange in t2g level as per the Hund’s rule.
The fourth electron can either enter into t2 g level to result in a
configuration of t2g4eg 0 or can enter the eg orbital to give a
configuration of t2g3eg 1.
Definition of Some Important Terms

Pertaining to Coordination Compounds
To understand the concept of coordination compounds better, it is

important to know certain terms and their definitions. Let’s take a look
at these terms and what they mean in coordination chemistry.
Coordination Chemistry
An assembly where a central atom or ion is bound to a fixed number

of molecules or ions is a coordination entity. For example, in the
coordination entity [CoCl3(NH3)3], the central cobalt ion is bound to
three ammonia molecules and three chloride ions surrounding it. Other
examples in coordination chemistry are [Ni(CO)4], [PtCl2(NH3)2],
[Fe(CN)6]4–, [Co(NH3)6]3+.
Browse more Topics under Coordination Compounds

● Bonding in Metal Carbonyls
● Crystal Field Theory
● Geometric and Optical Isomerism
● Importance and Applications of Coordination Compounds
● Introduction and Werner’s Theory of Coordination Compounds
● Isomerism in Coordination Compounds
● Nomenclature of Coordination Compounds
● Valence Bond Theory in Coordination Compounds
Central Atom/Ion
The atom/ion in a coordination entity that is bound to a fixed number

of ions/groups in a definite geometrical arrangement is the central
atom/ion. For example: In the coordination entities [NiCl2(H2O)4],
[CoCl(NH3)5]2+ and [Fe(CN)6]3–, the central atoms/ions are Ni2+,
Co3+ and Fe3+, respectively. These central atoms/ ions are also Lewis
acids.
Ligands
Ligands are the ions or molecules bound to the central atom/ion in a

coordination entity. These ions may be simple ions like Cl– or small
molecules such as NH3 or H2O. They may also be larger molecules
like H2NCH2CH2NH2 or N(CH2CH2NH2)3 or macromolecules such
as proteins.
Unidentate Ligands
In a lot of cases, only one atom in the ligand is bound to the metal ion.
In these cases, the ligand is unidentate. Examples of unidentate
ligands are H2O, NH3 or Cl–.
Bidentate Ligands
Ligands that bind to the metal ion through two donor atoms are
bidentate or didentate ligands. Examples are H2NCH2CH2NH2
(ethane-1,2-diamine) and C2O42– (oxalate).
Polydentate Ligands
Polydentate ligands are those that can bind to the metal ion through
several donor atoms. Examples are N(CH2CH2NH2)3 and
Ethylenediaminetetraacetate ion (EDTA4–). EDTA is an important
hexadentate ligand that can bind to a central metal ion through two
nitrogen and four oxygen atoms.
Ethylenediaminetetraacetic acid [Source: Wikipedia]
A di or polydentate ligand that uses two or more of its donor atoms to bind to a
single metal ion is a chelate ligand. The number of such donor groups is the
denticity of the ligand. These complexes are chelate complexes and are more
stable than other complexes containing unidentate ligands.
Ambidentate Ligands
Ambidentate ligands can ligate through two different atoms. Examples

are NO2– and SCN– ions where the NO2– ion can ligate with a central
metal atom/ion through nitrogen or oxygen and SCN– can ligate
through sulfur or nitrogen.
More Important Terms in Coordination Chemistry

Coordination Number
The number of ligand donor atoms to which the metal is directly
bound is the coordination number (CN) of the metal ion in the
complex. For example, the CN of Pt and Ni in the complex ions
[PtCl6]2– and [Ni(NH3)4]2+ are 6 and 4, respectively.
Likewise, the CN of Fe and Co in the complex ions [Fe(C2O4)3]3– and

[Co(en)3]3+ is 6 because both C2O42– and en (ethane-1,2-diamine) are
bidentate ligands.
Note: The CN of the central atom/ion is determined only by the

number of sigma bonds between the central atom/ion and the ligand,
not the Pi bonds.
Coordination Sphere
The coordination sphere consists of the central atom/ion and the

ligands attached to it. The ionizable groups, called counter ions are
written outside the bracket. For example, in the complex K4[Fe(CN)6],
[Fe(CN)6]4– is the coordination sphere and K+ is the counter ion.
Coordination Polyhedron
It refers to the geometric pattern or spatial arrangement of the ligands

directly attached to the central atom/ion. The most common polyhedra
are tetrahedral, octahedral and square planar. Examples:
[Co(NH3)6]3+ is octahedral, [Ni(CO)4] is tetrahedral and [PtCl4]2– is
square planar.
Oxidation Number of Central Atom
It is the charge the central atom would carry if all the ligands are
removed along with the electron pairs that are shared with it. It is
represented as the name of the coordination entity followed by the
oxidation number written in Roman numerals in parenthesis. For
example, in [Cu(CN)4]3–, the oxidation number of copper is +1 and is
Cu(I).
Homoleptic and Heteroleptic Complexes
Homoleptic complexes are complexes where a metal is bound to only

one kind of donor group whereas in heteroleptic complexes the metal
is bound to more than one kind of donor group. Examples –
[Co(NH3)6]3+ is homoleptic and [Co(NH3)4Cl2]+ is heteroleptic.
Solved Example on Coordination Chemistry
Question: Match the columns.
Ligand Example
(a) Unidentate (1) EDTA4–
(b) Bidentate (2) SCN–
(c) Polydentate (3) C2O4 2–
(d) Ambidentate (4) NH3
Solution: a-4, b-3, c-1, d-2.
Geometric and Optical Isomerism

You have come across the concept of allotropes in Chemistry, haven’t
you? Two elements with similar characteristics? In this chapter, we
will cover a concept quite relatable to this. It is the concept of
isomerism. We will also look at coordination number and its relation
to isomerism. We will start with the basic concept of what isomerism
is.
What is Isomerism?
Isomers are compounds having the same chemical formula but

different structural arrangements. We find a number of isomers due to
the variety of bond types and complicated formulae of many
coordination compounds. In the below chapter, we will discuss the
types of isomerism that these compounds exhibit.
1) Optical Isomerism
Optical isomers are those two compounds with the same chemical
formula such that their mirror images are not superimposable on each
other. Depending on the direction they rotate the plane of polarised
light in a polarimeter, we have two forms of optical isomers. They are:
● Dextro Isomer: This rotates to right.

● Laevo Isomer: This rotates to left.
Let us now look at the concept of geometric isomerism.
2) Geometric Isomerism
In case of disubstituted complexes, the substituted groups could either

be adjacent or opposite to each other. This leads to geometric
isomerism. Thus, we can prepare square planar complexes such as
[Pt(NH3)4Cl2] in two forms, cis and trans. When the chlorine atoms
are adjacent to each other, we get the cis form. While when two
chlorine atoms are opposite, we get the trans-form.
More about Geometric Isomerism and

Coordination Number
● We find this type of isomerism in heteroleptic complexes. The
main reason behind this would be the multiple geometric
arrangements of ligands around the central metal atom.
● Coordination compounds with the coordination number of 4
and 6 mainly exhibit this type of isomerism.
● Square planar complexes are coordination compounds with
coordination number 4 having [MX2L2] type formula, where X
and L are unidentate ligands. The two ligands X could either be
adjacent to each other in a cis isomer or opposite to each other
to form a trans isomer.
Square planar complexes with MABXL type formula show
three isomers-two cis and one trans.
● Tetrahedral geometry does not display these isomers. However,
octahedral complexes do show cis and trans isomerism. In
complexes with formula [MX2L4] type, we can have the X
ligands in the arrangement of cis or trans to each other.
● We also observe this type of isomerism when bidentate ligands
L–L [e.g., NH2 CH2 CH2 NH2 (en)] are present in complexes
with [MX2(L–L)2] type formula.
● There is another type of geometrical isomerism that we find in
octahedral coordination entities with [Ma3b3] type formula. An
example is [Co(NH3)3(NO2)3].
Q: What are facial and meridional isomers?
Ans: Facial isomers are those where the three donor atoms of the same
ligands occupy adjacent positions at the corners of an octahedral face.
They have the ligands in the cis arrangement. We get the meridional
isomers when the positions of the ligands are around the meridian of
the octahedron. One pair is in trans arrangement here.
Importance and Applications of

Coordination Compounds
So, why are we discussing so much about coordination compounds? Is

it just in theory or does it have any applications? Well, you would be
surprised to know how important these coordination compounds are in
real life. In this chapter, we will look at the importance and
applications of coordination compounds. We will look at the practical
applications of these important compounds.
Review of Organic Compounds
Coordination compounds are a class of compounds that we know as

the complex compounds. This is because of the chemistry that
involves these compounds. We have known enough about these
compounds already, including their structures and isomers etc.
We know that transition metals have this special property of forming

coordination complexes. This is due to the high charge to mass ratio
and also the availability of d-orbitals. The advances in coordination
chemistry provide various complex compounds that we use in various
industries. Coordination compounds are a common application in
various industries. These include mining & metallurgy, medical
sciences etc. to name a few.

● Definition of Some Important Terms Pertaining to
Examples and Types
Many of the biological compounds are coordination complexes. You

surely know of haemoglobin, chlorophyll, and vitamin B-12. Don’t
you? What do you think these are? These are nothing but complex
compounds.
There are numerous other coordination compounds that play an

important role in biological processes. Our body produces and
consumes many complex compounds during these physiological
processes.
Photosynthesis in plants requires chlorophyll for the process. This

chlorophyll is a magnesium-porphyrin complex. Many enzymes that
catalyse the life processes within our body are coordination
complexes. One such example is that of carboxypeptidase. It is a
coordination compound acting as an enzyme. It is necessary for
catalysing the process of digestion.
Applications of Coordination Compounds
● Coordination compounds have specific colours. Therefore, they

find a common place in industries for intense colourations.
Phthalocyanine is a class of coordination complexes that the
dyes and pigments industry extensively use. They use it to
impart specific colouration to fabrics.
● Some of the cyanide complexes find their use for electroplating
a protective layer on surfaces. There are complexes that find
the application of coordination compounds in photography.
● EDTA is another complex compound we use for the
determination of hardness of water. Uses of coordination
compounds also involve their application as catalysts. These
days, they are becoming increasingly popular in the polymer
industry as well.
● We apply the concept of coordination compounds in the
extraction of metals from their ores too frequently these days.
Extraction of nickel and cobalt involves uses a major use of
these compounds. These metals are extracted by
hydro-metallurgical processes requiring a lot of complex ions.
● As more and more coordination compounds are getting
synthesised, scientists and engineers are now having a wide
range of options for improving and optimising the processes
that require them.
Q: Why do we use coordination compounds to separate metals in

extractive metallurgy?
Ans: We generally use these compounds in the separation of metals

during the process of extractive metallurgy. This is because these
complex ions possess this specific property of selective precipitation
and solubility.
Introduction and Werner’s Theory of
Who is the father of coordination chemistry? Yes! The man in

question is none other than Werner. He is famous for his Werner’s
theory of coordination compounds. Are you aware of what this theory
is? In this chapter, we will study all about the theory and look at its
postulates and examples.
What is Werner’s Theory?
In 1823, Werner put forth this theory to describe the structure and
formation of complex compounds or coordination compounds. It is
because of this theory that he got the Nobel prize and is known as the
father of coordination chemistry. Are you ready to learn the important
postulates of this theory?

Postulates of Werner’s Theory
The important postulates of Werner’s theory are:
● The central metal or the metal atoms in coordination

compounds show two types of valency. They are the primary
and secondary valency.
● The primary valency relates to the oxidation state and the
secondary valency relates to the coordinate number.
● The number of secondary valences is fixed for every metal
atom. It means that the coordination number is fixed.
● The metal atom works towards satisfying both its primary and
secondary valencies. A negative ion satisfies the primary
valency. On the other hand, a negative ion or neutral molecules
satisfy secondary valencies.
● The secondary valencies point towards a fixed position in
space. This is the reason behind the definite geometry of the
coordinate compound. For example, let us consider the case of
a metal ion having six secondary valencies. These arrange
octahedrally around the central metal ion. If the metal ion has
four secondary valencies, these arrange in either tetrahedral or
square planar arrangement around the central metal ion.
Therefore, we see that the secondary valency determines the
stereochemistry of the complex ion. On the other hand, the
primary valency is non-directional.
Learn the Nomenclature of Coordination Compounds here.
Examples Based on Postulates of Werner’s

Theory
Werner’s theory is responsible for the formation of structures of

various cobalt amines. We will look at its explanation now. Cobalt has
a primary valency (oxidation state) of three and exhibits secondary
valency (coordination number) of 6. We represent the secondary
valencies by thick lines and the primary valency by broken lines.
1) CoCl3.6NH3 Complex: In this compound, the coordination number
of cobalt is 6 and NH3 molecules satisfy all the 6 secondary valencies.
Chloride ions satisfy the 3 primary valencies. These are
non-directional in character. These chloride ions instantaneously
precipitate on the addition of silver nitrate. The total number of ions,
in this case, is 4, three chloride ions and one complex ion.
2) CoCl3.5NH3 complex: In this compound, cobalt has the

coordination number of 6. However, we see that the number of
NH3molecule decreases to 5. The chloride ion occupies the remaining
one position. This chloride ion exhibits the dual behaviour as it has
primary as well as secondary valency.
3) CoCl3.4NH3 complex: In this compound, two chloride ions exhibit
the dual behaviour of satisfying both Primary and Secondary
Valencies. This compound gives a precipitate with silver nitrate
corresponding to only one Cl– ion and the total number of ions, in this
case, is 2. Hence, we can formulate it as [CoCl2(NH3)4]Cl.
Werner’s Theory and Isomerism
Werner turned his attention towards the geometrical arrangements of

the coordinated groups around the central cation. He was successful in
explaining the cause behind optical and geometrical isomerism of
these compounds. Some examples are as follows:
1) [CoCl2(NH3)4]Cl complex: According to Werner, there are three

structures possible for this complex. These are planar, trigonal prism,
octahedral. The number of possible isomers is 3 for planar, 3 for
trigonal prism and 2 for octahedral structure.
However, as we could isolate only two isomers of the compound, he

concluded that geometrical arrangement of the coordinated group
around the central atom in this compound was octahedral. In the case
of several other complexes in which the coordination number of the
central atom was six, Werner was of the opinion that in all these cases
the six coordinated complex have octahedral geometry.
He also read the geometry of the complexes where the coordination

number of the central metal atom is 4. He gave two possible structures
for such compounds: Square Planar and Tetrahedral. Let us look at an
example of the same.
2) [PtCl2(NH3)2] complex: In this complex, the coordination number

of the metal is 4. According to Werner, this complex exists in two
isomeric forms, cis and trans. This shows that all the four ligands lie in
the same plane. Therefore, the structure should be a square planar or
tetrahedral.
Learn more about Isomerism and its types.

Q: What are the limitations of Werner’s Theory?
Ans: Like all the major theories, Werner’s Theory was not free from
limitations. The common limitations of the theory are:
● It could not explain the inability of all elements to form

coordination compounds.
● The Werners theory could not explain the directional properties
of bonds in various coordination compounds.
● It does not explain the colour, the magnetic and optical
properties shown by coordination compounds.
Q. What is IUPAC name of [Fe(NH3)4O2C2O4]Cl?
Learn the Nomenclature of Coordination Compound to find the

answer.
Isomerism in Coordination Compounds

Certain compounds such as coordinates have an identical formula but
different properties and different structure. Even though they have the
same formula they carry different color. You might be wondering
which are these compounds. To know more about isomerism in
coordination compounds, let’s dig deep into this interesting topic in
the section below.
Isomerism in Coordination Compounds

What are Ligands?
A metal ion in a solution cannot exist in isolation but in combination

with ligands such as solvent molecules or simple ions that form
complex ions or coordination compounds. These complexes have a
central atom or ion which is often a transition metal.
These complexes also have a cluster of ion or neutral molecules

surrounding ligands that bond with a coordinated bond to a central
metal atom or ion. Ligands act as Lewis bases (electron pair donor) or
as Lewis acids (electron pair acceptor).
Complex Ions
The ability of metallic elements to act as Lewis acids that form metal
complexes with a variety of Lewis bases is their most important
property. A metal complex has a central metal atom or ion that bonds
to one or more ligands. These are the complex ions. A coordinate
compound contains one or more metal complexes.
Why are Coordination Compounds Important?
Mentioned below are three reasons explaining why coordination

compounds are essential.
● The periodic table has most of the elements that are metals, and
almost all metals form complexes.
● Many industrial catalysts are metal complexes and important to
control reactions.
● Transition metal complexes are essential in biochemistry.
Isomers
Isomers are two or more different compounds having the same

formula. There are two principal types of isomerism in coordination
compounds:
1. Stereo isomerism in coordination compounds

2. Structural isomerism in coordination compounds
Coordination compounds
What are Stereoisomers?
Stereoisomers are the isomers that have the same atoms, the same set
of bonds that differ only in the relative orientation of these bonds.
These are subdivided as follows:
● Geometrical isomerism: Geometrical isomers are possible for

square, planar, and octahedral complexes, but not tetrahedral.
● Optical isomerism: This isomerism is possible for both
tetrahedral and octahedral complexes, but not for square and
planar.
Source: Wikipedia
What are Structural Isomers?
Structural isomers are the isomers that have the same molecular
formula, that differ in the bonding patterns and atomic organization.
Structural isomerism is subdivided as below:
Source: Wikipedia
Coordination Isomerism
Here the compounds contain complex anionic and cationic parts

occurring by the interchange of some ligands from the cationic part to
the anionic part. For example,
[Co(NH3)6] [Cr(C2O4)3] isomer 1
[Co(C2O4)3] [Cr(NH3)6] isomer 2
Ionization Isomerism
Here, isomers occur because of the formation of different ions in a

solution. For example,
[PtBr(NH3)3]O2NO2 anion in solution
[Pt(NO2)(NH3)]Br anion in solution

However, both anions are necessary to balance the charge of the
complex. Moreover, the difference in both isomers is one ion directly
attaches to the central metal but the other does not.
Hydrate Isomerism
A well-known and the best example of this isomer is chromium

chloride, Cr Cl3.6H2O, which may contain 4, 5, or 6 co-ordinate
water molecules.
[CrCl2(H2O)4]Cl.H2O bright green
CrCl(H2O)5]Cl2.H2O grey-green
Cr(H2O)6]Cl3 violet
Solved Question For You
Question: What are the applications of coordination compounds?
Ans: Coordination compounds have the following applications.

● Dyes and pigments: Ancient Greeks used a red madder dye for
various purposes. A recent example is copper phthalocyanine,
which is blue.
● Analytical chemistry: Some coordination compounds are used
as reagents in the laboratory for color tests, gravimetric
analysis and complexometric titration and masking agents.
● Sequestering agents: We can get rid of objectionable ions in
industrial processes with coordination compounds.
● Extraction of metals: Leaching of metals is done from their
ores by the formation of stable complexes. For example, Ag
and An as complexes of cyanide ions.
● Bio-inorganic chemistry: Naturally occurring complexes are
hemoglobin, chlorophyll, vitamin B12, etc.
Nomenclature of Coordination
Compounds
Just like we know that nomenclature of organic compounds is

important, naming the various coordination or complex compounds is
also very important. Complex nomenclature is an extensive study and
as chemistry students, you must be well-versed with the same. In this
chapter, we will see how the various complex compounds get their
names. We will look at the few simple rules to follow for the same.
Complex Nomenclature
Why do we need to name the compounds? How would your teacher

call you and your best friend if you both didn’t have any names?
Similarly, the naming of coordination compounds(complex
nomenclature) is important to provide an unambiguous method to
represent and describe formulas and names of coordination
compounds systematically.
Also, it becomes very important while you deal with isomers. We

follow a few rules of the International Union of Pure and Applied
Chemistry (IUPAC) system while naming these compounds. In a
nutshell, the rules are as follows:
In Coordination Compounds,
● Within the coordination entities, we list down the central
atom/ion first followed by the ligands.
● After this, we list down the ligands in alphabetical order.
● We write the formula of coordination entity in square brackets.
● Ligand abbreviations are to be enclosed in parentheses.
● We must not keep any space between the ligands and the metal
within a coordination sphere.
● The charge on the cation(s) should be equal to the charge of the
anion(s).
Now, let us look at these rules of complex nomenclature in greater

details, along with suitable examples.

Rules of Complex Nomenclature

Rule 1
While naming a coordination compound, we always name the cation

before the anion. This rule does not count the fact of whether the
complexion is cation or anion. Let us understand this with the help of
an example.
Na[Co(NH)4 (Cl)2] → Na is to be named first followed by [Co(NH)4

(Cl)2]
Sodium tetramminedichlorocoblatate(I)
[Co(NH)4 (Cl)2]SO4 → [Co(NH)4 (Cl)2] is to be named first

followed by SO4
Tetraamminedichlorocobalt(0) sulphate.
Rule 2
When we see that there are multiple types of ligands present in any
coordination compound, we name the ligands in alphabetic order after
by the name of central metal atom/ion.
● Name of the anionic ligands ends with ‘o’.

For example, Chloride → Chlorido, Nitrate → Nitrito
● For neutral ligands, their common name is used as such e.g.
H2NCH2CH2NH2 → ethylenediamine
H2O → aqua
NH3 → ammine
CO → carbonyl
N2 → dinitrogen
O2 → dioxygen
Rule 3
If the names of the ligands have a numerical prefix, then we use the
terms like bis, tris, tetrakis. This will represent the ligand to which
they refer being placed in parentheses. For example, we name
[NiCl2(PPh3)2] as dichloridobis(triphenylphosphine)nickel(II)
Rule 4
After naming the ligand in alphabetic order, we name the central metal
atom/ion.
● If the complex ion is a cation, we name the metal same as the

element.
● If the complex is an anion, the name of metal ends with the
suffix -ate for Latin name.
Rule 5
We give the oxidation state of the metal in the complex as a roman

numeral in parentheses.
Rule 6
We name the neutral complex molecule similar to that of the complex
cation.
Rule 7
There are some ligands like NO2, CN that are attached to the central
metal atom/ion through different atoms. We name them as follows:
Thus, M-NO2 → nitro
M-ONO → nitrito
M-SCN → thiocyanato
M-NCS → isothiocyanato
Q: Write the IUPAC name of [Fe(NH3)4O2C2O4]Cl.
Ans: In this complex part has a charge of +1. The ligand oxalato has a
charge of –2, so iron should be in +3 state meaning O2 to be neutral.
O2 behaves as a neutral ligand and the IUPAC name is
Tetraammineoxalatodioxygeniron (III) chloride.
Valence Bond Theory in Coordination
Compounds
You must have studied that Werner’s theory for coordination

compounds failed. Do you remember why Werner’s theory for
coordination compounds failed? Well, it failed to explain many
critical aspects of valence electrons and directions in the coordination
compounds.
Then, how do we explain the structure of all these coordination

compounds? Yes, we use the Valence bond theory which came on to
replace the Werners theory. In this chapter, we will look at the valence
bond theory and its important postulates. In the end, we will also look
at the imitations of the valence bond theory.
What is the Valence Bond Theory?
One of the major drawbacks of Werner’s theory is its failure to

explain the coordination compounds’ directional properties. Valence
bond theory became successful in explaining the structure and bond
linkages in these coordination compounds.
So, what does the valence bond theory say? According to this theory,
the metal atom or ion under the influence of ligands can use its (n-1)d,
ns, np, nd orbitals for hybridisation. This would lead to a yield a set of
equivalent orbitals of definite geometry.
These include octahedral, tetrahedral, square planar and other such

geometrical arrangements. The hybridised orbitals can overlap with
the ligand orbitals. These orbitals are ready to donate valence
electrons / electron pairs for bonding.
Explanation of Valence Electrons in Valence Bond

Theory
We will understand the valence bond theory with the help of an

example. Let us consider the diamagnetic octahedral complex
[Co(NH3)6]3+. Here, the cobalt ion has the electronic configuration of
3d6. The hybridization scheme is as follows,
Orbitals of Co+3ion:
d2sp3 hybridised orbitals of Co3+ is as follows,
d2sp3 hybrid,
We can see that the compound does not contain any unpaired valence
electrons. Therefore, it is diamagnetic in nature. All the six pairs of
electrons from NH3 molecules occupy the six hybridized orbitals.
Since, the inner d orbital (3d) takes place in hybridisation, the

complex, [Co (NH3)6]3+ is what we call the inner orbital or low spin
or spin paired complex. The paramagnetic octahedral complex
generally uses outer orbital (4d) in hybridisation (sp3 d2). It is known
as outer orbital or high spin or spin-free complex.

Q: State the limitations of the valence bond theory.
Ans: The limitations of the valence bond theory are as follows:

● With the valence bond theory, we can not have a quantitative
interpretation of magnetic data. This is one major drawback of
the valence bond theory.
● The valence bond theory fails to explain the various colors that
the coordination compounds exhibit. This is also relatable to
the Werner theory.
● The valence bond theory does not give a quantitative
interpretation of the thermodynamic stabilities of the
coordination compounds. It does not also speak of the kinetic
stabilities of these compounds as well.
● The various predictions that the valence bond theory makes
regarding the tetrahedral and square planar structures of
4-coordinate complexes are not completely accurate.
● It does not draw any distinctive line between the weak and
strong ligands.

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Bonding in Metal Carbonyls

Brief about Metal Carbonyls

We are aware of many complex compounds having carbonyl ligands,

In a metal carbonyl, the metal-carbon bond has the characteristics of

The ​formation​ of a metal-carbon σ bond takes place because of the

The other form is the creation of a metal-carbon π bond because of the

Stability of Carbonyl Compounds

How stable are these coordination compounds? Well, we have

Quantitatively speaking, the stability of any complex is the magnitude

In the above example, the amount of AB​4​ molecule in the solution

Solved Example for You

Q: Write a note on the physical characteristics of carbonyl

Crystal Field Theory

According to this theory, the metal-ligand bond acts as an ionic bond

In case of an octahedral coordination compound, there are six ligands

It is the process of the splitting of degenerate level in the presence of

Solved Example for You

Q: How does the filling of d-orbitals take place, according to the

Ans: Filling of d-orbitals takes place as follows:

Definition of Some Important Terms

To understand the concept of coordination compounds better, it is

An assembly where a central​ atom​ or ion is bound to a fixed number

Browse more Topics under Coordination Compounds

The atom/ion in a coordination entity that is bound to a fixed number

Ligands are the ions or molecules bound to the central atom/ion in a

Ambidentate ligands can ligate through two different atoms. Examples

More Important Terms in Coordination Chemistry

Likewise, the CN of Fe and Co in the complex ions [Fe(C​2​O​4​)​3​]​3–​ and

Note:​ The CN of the central atom/ion is determined only by the

The coordination sphere consists of the central atom/ion and the

It refers to the geometric pattern or spatial arrangement of the ligands

Oxidation Number of Central Atom

Homoleptic and Heteroleptic Complexes

Homoleptic complexes are complexes where a metal is bound to only

Solved Example on Coordination Chemistry

Question: Match the columns.

(a) Unidentate (1) EDTA​4–

(b) Bidentate (2) SCN​–

(c) Polydentate (3) C​2​O4​ 2–

(d) Ambidentate (4) NH​3

Solution: a-4, b-3, c-1, d-2.

Geometric and Optical Isomerism

Isomers are compounds having the same ​chemical formula​ but

● Dextro Isomer: This rotates to right.

Let us now look at the concept of geometric isomerism.

In case of disubstituted complexes, the substituted groups could either

More about Geometric Isomerism and

Solved Example for You

Q: What are facial and meridional isomers?

Importance and Applications of

So, why are we discussing so much about coordination compounds? Is

Review of Organic Compounds

Coordination compounds are a class of compounds that we know as

We know that transition metals have this special property of forming

Browse more Topics under Coordination Compounds

Examples and Types

Many of the biological compounds are coordination complexes. You

There are numerous other coordination compounds that play an

Photosynthesis in plants requires chlorophyll for the process. This

The formation of a metal-carbon σ bond takes place because of the

In the above example, the amount of AB4 molecule in the solution

An assembly where a central atom or ion is bound to a fixed number

Likewise, the CN of Fe and Co in the complex ions [Fe(C2O4)3]3– and

Note: The CN of the central atom/ion is determined only by the

(a) Unidentate (1) EDTA4–

(b) Bidentate (2) SCN–

(c) Polydentate (3) C2O4 2–

(d) Ambidentate (4) NH3

Isomers are compounds having the same chemical formula but

Ans: We generally use these compounds in the separation of metals

Who is the father of coordination chemistry? Yes! The man in

Learn the Nomenclature of Coordination Compounds here.

2) CoCl3.5NH3 complex: In this compound, cobalt has the

Learn more about Isomerism and its types.

Q. What is IUPAC name of [Fe(NH3)4O2C2O4]Cl?

Learn the Nomenclature of Coordination Compound to find the

[Co(NH3)6] [Cr(C2O4)3] isomer 1

[Co(C2O4)3] [Cr(NH3)6] isomer 2

[PtBr(NH3)3]O2NO2 anion in solution

[Pt(NO2)(NH3)]Br anion in solution

[CrCl2(H2O)4]Cl.H2O bright green

Just like we know that nomenclature of organic compounds is

Na[Co(NH)4 (Cl)2] → Na is to be named first followed by [Co(NH)4

[Co(NH)4 (Cl)2]SO4 → [Co(NH)4 (Cl)2] is to be named first

We give the oxidation state of the metal in the complex as a roman

Thus, M-NO2 → nitro

Q: Write the IUPAC name of [Fe(NH3)4O2C2O4]Cl.