Coordination Compounds

Addition Compound

Compounds made up of two or more stable compounds by crystallization in a fixed

stoichiometric ratio are called addition compound. For example

KCl + MgCl2 + H2O ⟶ KCl.MgCl2.H2O

Addition compounds are of two types :

(i) Those which lose their identity in solution (double salt)

FeSO4.(NH4)2SO4.H2O ⟶ FeSO4 + (NH4)2SO4 + H2O

(ii) Those which retain their identity in solution (coordination or complex compounds)

Fe(CN)2 + 4KCN ⟶ K4[Fe(CN)6] (Potassium ferrocyanide)

2. Coordination Entity

It constitutes a central metal atom or ion bonded to a fixed number of ions or molecules with
coordinate bonds. For example, in coordination sphere (entity) of [CoCl 3(NH3)3], cobalt ion
(Co3+) is surrounded by three ammonia molecules and three chloride ions.

3. Central Atom/Ion

In coordination entity, the atom/ion to which a fixed number of ions/groups are attached in a
definite geometrical arrangement around it, is called central atom/ion. For example, in
K2[PtCl6], Pt+4 is central metal ion. Central metal atom or ion accepts lone pairs from the
ligands hence it acts as Lewis acid.

4. Ligands

The donor atoms, molecules or anions which donate a pair of electrons to the metal atom/ion
are called ligands. Hence ligands are Lewis bases. For example, in [Ni(NH 3)6]Cl2, NH3 is
ligand (Lewis base).

5. Coordination Number
It may be defined as number of coordinate bonds formed with central atom/ion by the
ligands. For example in coordination entity [Ag(CN) 2]–,[Cu(NH3)4]2+ and [Cr(H2O)6]3+, the
coordination number of Ag, Cu and Cr are 2, 4 and 6 respectively.

6. Coordination Polyhedron

The spatial arrangement of ligands around central metal atom/ion is called coordination
polyhedron. The most common coordination polyhedra are

7. Oxidation Number

Oxidation number of the central metal atom/ion in a complex is the charge present on it if all
the ligands are removed along with the electron pairs that are shared with central atom. It is
represented by Roman numerals in parenthesis after the name of central atom. For example,
oxidation number of Co, Fe and Ni in [Co(NH 3)6]3+, [Fe(CN)6]4– and [Ni(CO)4] is +3, +2 and
0, and written as Co(III), Fe(II) and Ni(0) respectively.

8. Homoleptic and Heteroleptic Complexes

Complexes which have only one type of ligands are homoleptic

e.g., [Co(NH3)6]3+

Complexes which have more than one type of ligands are heteroleptic

e.g., [Co(NH3)4Cl2]+ complexes.

Classification of Ligands

1. On the Basis of Charge on Ligands

(i) Anionic ligands (negatively charged ligands) e.g., F–, Cl–, CN–, S2–, SO42– etc.

(ii) Neutral ligands (uncharged and electron pair donor) e.g., CO, NH3, H2O etc.
(iii) Cationic ligands (positively charged ligands) e.g., NO+, NH2 – NH3+ etc.

2. On the Basis of Denticity

(i) Monodentate: Ligands having single donor atom, e.g., Cl -, H2O, NH3, NH2 – NH3+, etc.
(also called unidentate ligands).

(ii) Bidentate: Ligands can bind through two donor atoms (used simultaneously), e.g.,

(iii) Polydentate: Single ligands having several donor atoms, e.g., EDTA4- ion (hexadentate)

It can bind through two N and four O atoms to a central atom.

(iv) Ambidentate: Ligands which can bind through two different atoms (only one at a time)
to form coordinate bond, e.g., NO2-, SCN- etc.
(v) Flexidentate: Ligands having variable denticity, which depends upon nature of metal ion.
For e.g., EDTA having denticity 4 or 6.

3. On the Basis of Type of Donation of Lone Pair

(i) σ-donor: Ligands that donate lone pair and make σ-bond to central atom/ion, e.g., H 2O,
NH3 etc.

(ii) σ-donor π-acceptor: Ligands that donate lone pair to central atom/ion by making σ-bond
and accept appreciable amount of electron density from metal atom/ion into its vacant π or π*
orbital, e.g., CO, NO etc. (these are also called π-acid ligands).

(iii) π-donor π-acceptor: Ligands that donate and accept π-electrons through π +-bonds with
central atom/ion, e.g., HC ☰ CH, C2H4, C6H6 etc.

4. List of Ligand
IUPAC Nomenclature of Coordination Compounds

Coordination compounds are formulated and named according to the system set up by
IUPAC (International Union of Pure and Applied Chemistry). It is important for writing
systematic names and formulas, particularly when dealing with isomers.

1. Rules for Writing Formulae of Mononuclear Coordination Entities

It is very convenient to get information about constitution of a compound if we know the

formula, mononuclear entities contain a single central atom. To write the formula, following
rules are applied:

1. The central atom is listed first.

 2. Ligands are then listed in alphabetical order and their placement does not depend on
their charge.
3. In case of abbreviated ligands (polydentate) the first letter of abbreviation is used to
determine the position of ligand in alphabetical order.
4. Entire coordination entity is enclosed in square brackets, whether charged or not.
Polyatomic ligands are enclosed in parenthesis, and also their abbreviations.
5. No space is left in between names of ligands and central atom/ion.
6. When the formula of a charged coordination entity is to be written without counter
ion, the charge is indicated outside square bracket as a right superscript, with the
number before sign. For e.g., [Co(CN)6]3–, [Cr(H2O)6]3+, etc.
7. Charge on cation and anion is counter balanced.

2. Rules for Naming of Mononuclear Coordination Compounds

Following rules are applied for naming of coordination compounds:

1. Positive part of complex compounds will be named first, followed by negative part.
2. Ligands are named first in alphabetical order, followed by central atom (reverse in
case of writing formula).
3. Prefixes mono, di, tri, tetra etc. are used to indicate number of ligands.

Prefixes bis, tris, tetrakis are used for complex ligands (including a numerical prefix).
For example, [NiCl2(en)2]SO4 is named as dichloridobis (ethylene diamine) nickel (II)
sulphate.

4. Name of anionic ligands end with ‘o’, cationic ligands end with ‘ium’.

For neutral ligands regular names are used except ‘aqua’ for H 2O, ‘ammine’ for NH3,
‘nitrosyl’ for NO, ‘carbonyl’ for CO. These are placed within ( ).

5. Oxidation state of central atom/ion is indicated in roman numerals in bracket after the
name of metal.
6. When coordination entity has negative charge, then name of central metal ends with
‘ate’, otherwise not. For e.g., in [Fe(CN)6]4-, ferrate is used for Fe.

Examples:

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

(b) [Ni(NH3)6]Cl2 – Hexaamminenickel (II) chloride

(c) [Ni(CO)4] – Tetracarbonylnickel (0)

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

(e) [Mn(H2O)6]2+ – Hexaaquamanganese (II) ion

(f) K2[Ni(EDTA)] – Potassium ethylenediamminetetraacetatonickelate (II)

(g) [Pt(NH3)4][PtCl4] – Tetraammine platinum (II) tetrachloridoplatinate (II)

Name of the bridging groups : If a complex contains two or more central metal atoms or
ions, it is termed as polynuclear. In certain polynuclear complexes, ligands may link the two
metal atoms or ions. Such ligands which link the two metal atoms or ions in polynuclear
complexes are termed as bridge ligands. These bridge ligands are separated from the rest of
the complex by hyphens and denoted by the prefix. If there are two or more bridging groups
of the same kind, this is indicated by di–μ–, tri–μ– etc.
[(NH3)5] Co – NH2 – Co(NH3)5](NO3)5 ;
μ-amidobis [pentaamminecobalt (III)] nitrate
[(NH3)5Co – OH – Co(NH3)5] Cl5
μ-hydroxobis [pentaamminecobalt (III)] chloride
[(CO)3Fe(CO)3Fe(CO)3]
Tri-μ carbonylbis [tricarbonyliron (0)]
[Be4O(CH3COO)6]
Hexa-μ-acetato (O,O)- μ-oxotetraberyllium (II)

(7) If any lattice component such as water or solvent of crystallisation are present, these
follow the name and are preceded by the number of these groups (molecules of solvent of
crystallisation) in Arabic numerals.
For example,
[Cu(H2O)4]SO4. H2O
Tetraaquacopper (II) sulphate 1-water
[Cr(H2O)4Cl2]Cl.2H2O
Tetraaquadichlorochromium (III) chloride 2-water

Valence Bond Theory In Coordination Compounds

The valence bond theory was proposed by Linus Pauling in 1928 .
The Main Assumptions of this Theory are:

(1) The central metal ion in the complex makes available a number of empty orbitals for the formation
of coordination bonds with suitable ligands. The number of empty orbitals made available for this
purpose is equal to coordination number of the central metal ion.
For example: If coordination number is 6 , six empty orbitals are made available and if coordination
number is 4, four empty orbitals are made available in the central metal ion.

(2) The appropriate atomic orbitals (s, p and d) of the metal hybridise to give a set of equivalent
orbitals of definite geometry such as square planar, tetrahedral, octahedral and so on.
(3) The d-orbitals involved in the hybridisation may be either inner d-orbitals i.e. (n – 1) d or outer d-
orbitals i.e. nd. The complex formed by inner (n-1) d-orbitals, is called inner orbital complex whereas
the complex formed by outer d-orbital is called outer orbital complex.

(4) Each ligand has at least one orbital (of donor atom) containing a lone pair of electrons. Pauling
classified the ligands into two categories (i) Strong ligands like CN –, CO– etc. (ii) weak ligands like
F–, Cl– etc.

(5) The empty hybrid orbitals of metal ion overlap with the filled orbitals of the ligand to form metal-
ligand coordinate covalent bonds.

(6) The spin only formula is used to compute a complex’s magnetic moment.

M = √[n(n+2)] BM
Where n = Number of unpaired electrons in complex compound and BM = Bohr Magneton

Applications of Valence Bond Theory

Inner and Outer Orbital Complexes

In octahedral structures, the central metal may use inner (n-1)d orbitals or outer nd-orbitals
for hybridisation. Therefore, the complexes may be classified as :

(i) Inner orbital complex or entity

If the complex is formed by the use of inner d-orbitals for hybridisation (written as d 2sp3), it is
called inner orbital complex. In the formation of inner orbital complex, the electrons of the metal
are forced to pair up and hence the complex will be either diamagnetic or will have lesser number of
unpaired electrons. Such a complex is also called low spin complex.

For example, [Fe(CN)6]3- and [Co(NH3)6]3+ are inner orbital complexes.

(ii) Outer orbital complex or entity

If the complex is formed by the use of outer d-orbitals for hybridisation, it is called an outer
orbital complex. The outer orbital complex will have larger number of unpaired electrons
since the configuration of the metal ion remains undisturbed. Such a complex is also
called high spin complex.For example, [Fe(H2O)6]3+ and [CoF6]3- are outer orbital complexes.

Examples of Complexes of C.N. = 6

(1) [Cr(NH3)6]3+ complex

The chromium (Z = 24) has the electronic configuration 3d5 4s1

The chromium in this complex is in +3 oxidation state and the ion is formed by the loss of one 4s and
two of the 3d-electrons.
The inner d-orbitals are already vacant and two vacant 3d, one 4s and three 4p-orbitals are hybridised
to form six d2sp3 hybrid orbitals. Six pairs of electrons one from each NH3 molecule (shown by xx)
occupy the six vacant hybrid orbitals. The molecule has octahedral geometry.
Since the complex contains three unpaired electrons, it is paramagnetic.

(2) [Co(NH3)6]3+ ion

Cobalt atom (Z= 27) has the electronic configuration 3d74s2. In this complex, cobalt is in +3 oxidation
state and has the electronic configuration 3d6. This complex has been found to be diamagnetic. The
two electrons in 3d-orbitals are paired up leaving two 3d-orbitals empty. These six vacant orbitals
(two 3d, one 4s and three 4p) hybridise to form d2sp3 hybrid orbitals. Six pairs of electrons two from
each NH3 molecules are donated to these vacant hybrid orbitals. Thus, the complex has octahedral
geometry and is diamagnetic.

(3) [CoF6]3– complex ion

Cobalt is in +3 oxidation state and has the electronic configuration 3d 6. This complex has been found
to be paramagnetic due to the presence of four unpaired electrons.
The electrons in 3d-orbitals are not disturbed and the outer 4d-orbitals are used for hybridisation. The
six orbitals (one 4s, three 4p and two 4d) are hybridised forming six sp3d2 hybrid orbitals.

Six pairs of electrons, each one from F ion are donated to the vacant hybrid orbitals forming Co-F
bonds.

Thus, the complex has octahedral geometry and is paramagnetic.

(4) [Fe(CN)6]3- complex

Iron atom (Z = 26) has the electronic configuration 3d64s2. In this complex, iron is in +3 oxidation state
and has the electronic configuration 3d5.
The complex has one unpaired electron. The two electrons in 3d-orbitals are paired up leaving two 3d-
orbitals empty. These six vacant orbitals (two 3d, one 4s and three 4p) hybridise to form d²sp³ hybrid
orbitals. Six pairs of electrons one from CN¯ ion (shown by xx) occupy the six vacant hybrid orbitals.

The molecule has octahedral geometry and is paramagnetic due to the presence of one unpaired
electron.
Since the inner d-orbitals are used in hybridisation, the complex [Fe(CN) 6]3- is called an inner orbital
or low spin or spin paired complex.

(5) [Fe(H2O)6]3+ ion

Iron is in +3 oxidation state and has the electronic configuration as 3d5. The electrons in 3d-orbitals
are not disturbed and the outer 4d-orbitals are used for hybridisation.
The six orbitals (one 4s, three 4p and two 4d) are hybridised resulting sp3d2 hybridisation. Six pairs of
electrons, one from each water molecule occupy the six hybrid orbitals. The molecule is octahedral.
Since [Fe(H2O)6]3+ uses outer orbital (4d) in hybridisation, it is therefore, called outer orbital or high
spin or spin free complex.
This complex has been found to be paramagnetic due to the presence of five unpaired electrons.

(6) [Fe(CN)6]4- ion

Iron is in +2 oxidation state. The complex is diamagnetic and therefore, it involves

d2sp3 hybridisation.It is an inner orbital or low spin complex.

Examples of Complexes of C.N. = 4

Ni(II), Pt(II) and Pd(II) form mostly, the 4-coordinate entities.

The geometry will be tetrahedral or square planar depending upon whether sp3 or
dsp2 hybridisation is involved.

(i) [Ni(CN)4]2- ion

The nickel atom has the ground state electronic configuration as 3d 84s2.
Nickel is in +2 oxidation state and its electronic configuration is 3d 8.
Depending upon the type of hybridisation, there are two possible ways in which the complexes of
nickel with coordination number 4 may be formed.

(a) If the complex involves sp3 hybridisation, it would have tetrahedral structure : For the
formation of tetrahedral structure the 3d-orbitals remain unaffected and, therefore, the two unpaired d-
electrons remain as such. The complex would be paramagnetic.

(b) If the complex involves dsp2 hybridisation, it would have square planar structure The
formation of square planar structure through dsp2 hybridisation, one of the 3d-orbitals should be
empty and available for hybridisation. This is possible, if the two unpaired d-electrons are paired up
thereby making one of the 3d-orbitals empty. There is thus no unpaired electron and the complex
would be diamagnetic.

(ii) [NiCl4]2- ion

The nickel (II) ion has two unpaired electrons. The magnetic measurements of the complex
[NiCl4]2- show that it is paramagnetic and has two unpaired electrons. Therefore, in this case the 3d-
orbitals remain undisturbed and sp3 hybridisation occurs resulting in tetrahedral structure of the
complex. There are two unpaired electrons in the complex.
(iii) [Ni(CO)4]

The nickel (0) has 3d84s2 as its outer electronic configuration. For complexes with
coordination number 4, the central atom may involve sp3 or dsp2 type of hybridisation, for
each of which the 4s-orbital must be empty. The electrons of 4s orbitals are forced into 3d-
orbitals to pair up with the two unpaired d electrons. Therefore, the complex is diamagnetic.
This results in sp3 hybridisation and the complex has tetrahedral structure.

Examples of Complexes of C.N. = 5

(i) Fe(CO)5

The oxidation state of iron in this complex is zero and it has the outer electronic configuration as
3d6 4s2.According to the Hund’s rule, the six electrons shall occupy the five 3d orbitals in such a way
that there are four unpaired electrons. For the complexes with coordination number 5, the central atom
may involve dsp3 hybridisation, and the 4s orbital must be empty.
The two electrons of 4s orbital and one electron 3d orbital are pushed into 3d orbitals to pair up with
the three unpaired 3d electrons. The metal atom involves dsp3 hybridisation (one 3d, one 4s and three
4p) to give vacant dsp3 hybrid orbitals.
Since the complex has no unpaired electron, it will be diamagnetic and it is in agreement with
experimental results. Thus, the complex [Fe(CO)5] has trigonal bipyramidal geometry and is
diamagnetic.

Limitations of Valence Bond Theory

(i) It gives only the qualitative explanations for complexes.

(ii) It does not explain the detailed magnetic properties of the complexes.

(iii) This theory does not explain the colour and spectral properties of the coordination compounds.

(iv) It does not explain the thermodynamic and kinetic stabilities of different coordination
compounds.

(v) It does not make exact predictions regarding the tetrahedral or square planar structures of 4-
coordinate complexes.

(vi) It does not distinguish between weak and strong ligands.