GD GOENKA PUBLIC SCHOOL, GWALIOR

Subject: Chemistry
Class XII
Chapter : VI
Coordination Compounds
Definitions of Some Important Terms
1. 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
[CoCl3(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(NH3)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(NH 3)6]3+ and
have more than onetype 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., EDTA 4- 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.,
H2O, 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 paranthesis, 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 brackett
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.

The following examples will make the rules more clear:

(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)
Werner’s Theory of Coordination Compounds
To explain these properties, Werner proposed following postulates:
1. Each metal ion possesses two types of valencies:
(a) Primary valency (principle or ionizable)
(b) Secondary valency (subsidiary or non-ionizable)
2. Primary valency: These are normally ionizable and are satisfied by anions
only.
3. Secondary valency: These are non-ionizable, and are satisfied by ions or
neutral electron pair donor molecules (i.e., ligands). It represents coordination
number of central metal atom/ion.
4. Primary valencies are non-directional while secondary valencies are
directional.
5. Geometry of complex is decided by secondary valency. Thus, [Co(NH 3)6]3+,
[CoCl(NH3)5]2+ and [CoCl2(NH3)4]+ are octahedral entities, while [Ni(CO)4] and
[PtCl4]2- are tetrahedral and square planar respectively.
Effective Atomic Number
Transition metals form coordination compounds very readily because they have
vacant 'd' orbitals which can accommodate electron pairs donated by ligands. Metal
ion in the complex tends to attain nearest stable inert gas configuration by gaining
electrons from ligands. Generally, this is krypton (Z = 36).
Effective atomic number (EAN) of metal in a complex is given by:
EAN = Z–(O.N.) + 2(C.N.) or number of lone pairs donated to central atom.
where Z = atomic number
O.N. = oxidation number
C.N. = coordination number
Bonding in Coordination Compounds
The bonding features in coordination compounds was first described by Werner’s
theory. A lot of theories were introduced to explain the nature of bonding in
coordination compounds, like Valence Bond Theory (VBT), Crystal Field Theory
(CFT), Ligand Field Theory (LFT) and Molecular Orbital Theory (MOT).
(1) Valence Bond Theory (VBT)
According to this theory, the metal atom or ion can use (n–1)d, ns, np, nd orbitals for
hybridisation under the influence of ligands to yield a set of equivalent orbitals of
definite geometry such as square planar, tetrahedral, octahedral and so on. These
hybrid orbitals and ligand orbitals are allowed to overlap with each other that latter
can donate electron pair for bonding.
For (n–1)d orbitals used in hybridisation, there is formation of inner orbital complex,
and for np or nd orbitals the outer orbital complex formation takes place. Generally
inner orbital complexes are low spin complexes with lesser number of unpaired
electrons while outer orbital complexes are generally high spin complexes with more
numbers of unpaired electrons.
(2) Limitations of Valence Bond Theory
The following limitations of VBT are :
1. Does not give quantitative interpretation of magnetic data.
2. Does not explain colour of coordination compounds.
3. Does not give quantitative interpretation of kinetic or thermodynamic stabilities
of coordination compounds.
4. Cannot determine exact predictions regarding tetrahedral and square planar
complexes in C.N. = 4
5. Does not differentiate weak and strong ligands.
(3) Crystal Field Theory (CFT)
1. Anionic ligands are treated as negative point charges and neutral ligands as
point dipoles.
2. Interaction between metal atom and ligand is purely electrostatic. There is no
intermixing of atomic orbitals or no insertion of electron in metal orbitals.
3. If the field produced by surrounding ligand is symmetrical then d-orbitals of
metal is degenerate. But in most of complexes, degeneracy is lost because field
produced by ligand is not symmetrical and all dorbitals are not equally affected
by ligand field.
4. Loss of degeneracy leads to splitting of d-orbitals and in their energies, called
crystal field splitting (CFS).
(i) Crystal field splitting in octahedral coordination entities Six ligands are
surrounded to metal atom/ion. Since eg orbitals are more directional towards orbitals,
they experience greater repulsion and their energy is higher. t 2g orbitals lie away from
ligands, hence they have lesser repulsion and lower energy.
(ii) Crystal field splitting in tetrahedral coordination entities Coordination number
and number of ligands = 4. t2g set have higher energy than eg set as t 2g orbitals are
more closer to the direction of approach of ligands.

(4) Limitations of CFT

1. Assuming ligands as point charges, it follows that anionic ligands should exert
the greatest splitting effect. The anionic ligands actually found at low end of
spectrochemical series.
2. It does not explain the covalent character of bonding between ligand and
central atom.

Importance and Application of Coordination Compounds

 1. Detection and estimation of metal ions in qualitative and quantitative analysis.
For example, EDTA, DMG, α-nitroso-β-naphthol, cupron, etc. give colour
reactions.
2. Hardness of water is estimated by titration of Ca 2+ and Mg2+ with Na2EDTA,
and their estimation can be done due to difference in their stability constants.
3. Extraction of metals like silver and gold make use of complex compounds. For
e.g., gold forms[Au(CN)2]- in aqueous solution and can be separated in metallic
form by addition of zinc.
4. Purification of metals through formation and subsequent decomposition of
coordination compounds. For example Ni (impure) is converted to [Ni(CO) 4],
decomposed to pure nickel.
5. In biological systems, pigments responsible for photosynthesis, chlorophyll is a
complex of Magnesium. Haemoglobin, the red blood pigment of blood (oxygen
carrier) is complex of iron. Vitamin B 12, cyanocobalmine, the anti-pernicious
anaemia factor, is complex of cobalt.
6. Complexes, like rhodium complex, [(Ph3P)3RhCl], a Wilkinson’s catalyst, is
used for hydrogenation of alkenes.
7. Articles can be electroplated with silver and gold much more smoothly and
evenly from solution of complexes, [Ag(CN)2]- and [Au(CN)2]- than from a
solution of simple metal ions.
8. The developed film in black and white photography is fixed by washing with
hyposolution which dissolves the undecomposed AgBr to form complex,
[Ag(S2O3)2]3-.
9. Chelate therapy is used in medicinal industry. For example, EDTA is used in
treatment of lead poisoning. Growth of tumours can be inhibited by some
complexes of platinum, e.g., cis-platin [PtCl2(NH3)2] andrelated compounds.
Summary
1. Coordination compounds: Compounds formed due to combination of two or
more simple stable salts, which retain their identity in solution (dissolved state)
as well as solid.
2. Ligands: The donor atoms, molecules or anions which donate a pair of
electrons to metal atom/ion.
3. Coordination entity: It constitutes a central metal atom/ion bonded to a fixed
number of ligands with coordinate bonds.
4. Primary valency: Normally, it is ionizable valency and satisfied by anions
only.
5. Secondary valency: Non-ionizable valency, satisfied by ligands only.
6. Structural isomerism: It is shown by compounds that have different ligands
within coordination entity.
7. Stereoisomerism: It is due to different spatial arrangement of ligands around
metal.
8. Valence Bond Theory (VBT): According to this theory, the metal atom/ion
can use (n–1)d, ns, np, nd orbitals for hybridisation, under the influence of
ligands, to yield a set of equivalent orbitals, in definite geometry.
9. Crystal Field Theory (CFT): CFT is an electrostatic model which describes
electronic structure of metal ion in ionic crystals.
10. CFSE (Δ): Difference between energies of eg orbitals and t2g orbitals is
called crystal field stabilization energy.
11. Spectrochemical series: Series in which ligands are arranged in order of
increasing field strength.
12. Metal carbonyls: Complexes formes by most of transition metals with carbon
monoxide through both σ- and π-bonds, to form homoleptic carbonyls.
13. Synergic bonding: Bonding between metal and ligand due to donation of
electron pair from ligand to metal atom/ion and acceptence of electron pair
from d-orbital of metal to ligand.