Coordination Chemistry

Complex salts: These are the salts that contain at least one complex radical. These are the
compounds in which the central metal atom or ion is linked with coordinate bonds with
surrounding species that are rich in electrons. The complex ions retain their identity in solid
state as well as in dissolved state. e.g., Potassium ferrocyanide, K4 [Fe(CN)6].

Double Salts
These are the addition molecular compounds which are stable in solid state but dissociate into
constituent ions in the solution. e.g., Mohr’S salt, FeSO4·(NH4)2SO4 .6H2O is dissociated into
Fe2+, NH+4 and SO2-4 ions. So, they give all constituent ions upon dissolution.
Other examples are carnallite KCl.MgCl2.6H2O, potas alum K2SO4. Al2(SO4)3.24H2O etc.
Terms Related to Coordination Compounds
1. Complex ion or Coordination Entity
It is an electrically charged species in which central metal atom or ion is surrounded by
number of ions or neutral molecules.

(i) Cationic complex entity It is the complex ion which carries positive charge. e.g.,
[Pt(NH3)4]2+
(ii) Anionic complex entity It is the complex ion which carries negative charge. e.g.,
[Fe(CN)6]4-
2. Central Atom or Ion
The metal atom or ion to which a fixed number of ions or groups are bound is called central
atom or ion. It behaves as Lewis acid. e.g., in [(NiCI2(H2O)4]. Ni is central metal atom.
3. Ligands
Ligands are electron donating species (ions or molecules) bound to the central atom in the
coordination entity.
These may be charged or neutral. Ligands are of the following types:

(i) Monodentate It is a ligand, which has one donor site, i.e., the ligand bound to a metal ion
through a single donor site. e.g., H2O, NH3, etc.
(ii) Bidentate It is the ligand. which have two donor sites.

Dimethyl glyoxime (DMG)

(generally bidentate)

(iii) Polydentate It is the ligand, which have several donor sites. e.g., ethylene diamine
tetraacetate ion [EDTA]4- is hexadentate ligand.

Diethylene triamine (dien) (tridentate),

Triethylene tetramine (trien) tetradentate etc.

(iv) Ambidentate ligands These are the monodentate ligands which can ligate through two
different sites, e.g., NO-2, SCN–, etc.
(v) Chelating ligands: Bidentate or polydentate ligands which cause cyclisation around the
metal atom or ion by coordinate bonds are called chelate ligands. They use two or more
donor atoms to bind a single metal atom or ion. This phenomenon is called chelation and the
stabilisation of coordination compounds due to chelation is known as chelate effect.
(vi) Chelates: The complexes with chelate ring are called chelates or chelate complexes.
eg. Ethylene diamine copper(II) chloride

or [Cu(en)2] Cl2
4. Coordination Number
It is defined as the number of coordinate bonds formed by central metal atom, with the
ligands.

e.g., in [PtCI6]2-, Pt has coordination number 6.

In case of monodentate ligands,

Coordination number = number of ligands

In polydentate ligands.

Coordination number = number of ligands X denticity

5. Coordination Sphere
The central ion and the ligands attached to it are enclosed in square bracket which is known
as coordination sphere. The ionisable group written outside the bracket is known as counter
ions.

6. Coordination Polyhedron
The spatial arrangement of the ligands which are directly attached to the central atom or ion,
is called coordination polyhedron around the central atom or ion.
7. Oxidation Number of Central Atom
The charge of the complex if all the ligands are removed along with the electron pairs that are
shared with the central atom, is called oxidation number of central atom.

e.g., [Cu(CN)4]3- , oxidation number of copper is +1, and represented as Cu(I).

IUPAC Naming of Complex Compounds

Naming is based on set of rules given by IUPAC.

1. Name of the compound is written in two parts (i) name of cation, and (ii) name of anion.

2. The cation is named first in both positively and negatively charged coordination
complexes.

3. The dissimilar ligands are named in au alphabetical order before the name of central metal
atom or ion.
4. For more then one similar ligands. the prefixes di, tri, tetra, etc are added before its name.
If the di, tri, etc already appear in the complex then bis, tris, tetrakis are used.

5. If the complex part is anion, the name of the central metal ends with suffix ‘ate’.

6. Names of the anionic ligands end in ‘0’, names of positive ligands end with ‘ium’ and
names of neutral ligands remains as such. But exception are there as we use aqua for H2O,
ammine for NH3, carbonyl for CO and nitrosyl for NO.
7. Oxidation state for the metal in cation, anion or neutral coordination compounds is
indicated by Roman numeral in parentheses.

8. The name of the complex part is written as one word.

9. If the complex ion is a cation, the metal is named same as the element.

10. The neutral complex molecule is named similar to that of the complex cation.

Some examples are

(i) [Cr(NH3)3(H2O)3]Cl3
Triamminetriaquo chromium(III) chloride
(ii) [Co(NH2CH2CH2 NHCH2H2)3]2(SO4)3
tris (ethane-l,2-diamine) cobalt (III) sulphate

(iii) [Ag(NH3)2] [Ag(CN)2]

diamminesilver (I) dicyanoargentate(I)

(iv) K4 [Fe(CN)6]
potassium hexacyanoferrate (II)

Werner’s Coordination 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 is equal to the charge or oxidation state of metal ion, and it is also
called ionisable valency.

• Secondary valency is non ionisable valency and it is equal to the coordinate number of
central atom or ion.

• Secondary valency is fixed for every central atom or ion. It means that the coordination
number is fixed.

• The metal atom or ion satisfies both its primary and secondary valencies. Primary valency
is always satisfied by negative ions and secondary valency can be satisfied by ion or neutral
molecules. It means, negative ion can satisfy both primary and secondary valencies.

• The secondary valencies are directional in nature or they are pointed towards a fixed
position in space. So, they determine geometry and isomerism in complex compounds. But,
primary valency is non directional in nature.
• Secondary valency to the central atom or ion is represented by solid thick line and the
primary valency is shown by dotted lines.

Consider cobalt(II) amine complexes in which primary valency is 3 and secondary valency or
C.N. is 6. Cobalt has a primary valency (oxidation state) of three and exhibits secondary valency
(coordination number) of 6.
1) CoCl3.6NH3 Complex: In this compound, the coordination number of cobalt is 6 and
NH3 molecules satisfy all six secondary valencies. Chloride ions satisfy the 3 primary valencies.
These are non-directional in character. It is ionised to give three chloride ions and one
[Co(NH3)6]+3 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.

It ionises to give two chloride ions and [Co (NH3)5Cl] +3 complex ion.

3) CoCl3.4NH3 complex: In this compound, two chloride ions exhibit the dual behaviour of
satisfying both primary and secondary valencies. It ionises to give only one Cl– ion and
[Co(NH3)4Cl2]+3 complex ion.
Limitations of Werner’s Coordination Theory

• It does not explain why all metals cannot form coordination compounds.

• It does not explain the directional properties of bonds in various coordination compounds.

• It does not explain the colour, the magnetic and optical properties, and bonding in
coordination compounds.

Effective atomic number (EAN)

It is number that represents the total number of electrons surrounding the nucleus of a metal
atom or ion in a complex. It is the sum of all electrons from metal atom or ion and the bonding
electrons from the surrounding electron-donating atoms and molecule.

Consider the complex [Co(NH3)6]3+ . Here the number of electrons in the trivalent cobalt ion
Co+3 = 24 and the number of bonding electrons from six surrounding ammonia molecules, each
of which contributes one electron pair = 2 × 6 =12. So, EAN = 24+12 =36 (equal to electrons
in nearest inert gas Kr)

Sidgwick observed that the metal atom tends to surround itself with sufficient number of
ligands so that EAN is equal to the atomic number of nearest inert gas found in the same period
in which the metal is situated. The EAN rule is often referred to as the “18-electron rule” since
the total number of valence electrons (6 for Co3+ and 2 × 6 = 12 for 6 NH3) is 18.

In ferrocyanide complex ion [Fe (CN)6]-4, number of electrons in Fe+2 = 24 and number of
elctrons donated by six cyanide ions = 12. So, EAN= 24+12 = 36 (Kr configuration).
In [Ni(CO)4], E.A.N. = Number of electrons in Ni + number of electrons donated by CO groups
= 28 + 8 = 36.

In [Pt (NH3)6]4+, E.A.N. = number of electrons in Pt 4+ + number of electrons donated by six

ammonia molecules = 78 – 4 + 12 = 86 ie equal to atomic number of Radon (Ra).

EAN equal to the number of electrons in nearest inert gas is obeyed by most of the complexes.
But, in some complexes, EAN is close but not equal to the atomic number of nearest inert gas.
For example, in [Fe (CN)6]-3,

EAN = number of electrons in Fe+3 + number of electrons donated by six cyanide ions

= 23 + 12 = 35

In [PdCl4] 2- , E.A.N. = 46 – 2 + 8 = 52 (close but not equal to Atomic Number of Xenon (Xe)
ie 54). Such complexes which do not obey EAN rule are less stable.

Sidgwick Model

This is the model based on EAN given by Sidgwick. According to this model, the central atom
or ion accepts electron pairs from the surrounding ligands or electron rich species until it
achieves the EAN equal to atomic number of nearest inert gas, and gets stabilized. The metal
atom or ion makes coordinate covalent bonds towards it. The number of coordinate bonds
determines stability of the complexes.

For example, the Sidgwick model of [Cu (NH3)4] +2 is as shown:

Limitations of Sidgwick Model: -

1) Many complexes are quite stable even though they do not obey E.A.N. rule.
2) The ligand donates electron pair and metal accepts them. Due to this transfer of electrons,
negative charge on metal ion increases and the decrease in stability of complex due to this
process is not explained by this model.

3) It does not explain geometry of complexes.

Merits:

1) This theory can easily predict the co-ordination number of central metal atom or ion.

2) It explains the stability of complexes.

Valence Bond Theory (VBT) of complexes

This theory was proposed and developed by Linus Pauling to explain the structure and
magnetic properties of coordination compounds. The postulates of VBT of complexes are given
below:
1. The central metal atom (or) ion makes the required number of vacant orbitals available for
accommodating the electrons donated by the ligands.
2. The number of vacant orbitals is equal to the coordination number of the metal atom or ion
for the given complex.
3. The vacant orbitals of the metal atom (or) ion undergo a suitable type of hybridisation to
yield a set of equivalent hybrid orbitals of definite geometry. So, the geometry of complex is
determined by the mode of hybridization in central metal atom or ion.
Mode of hybridization Geometry
sp3 tetrahedral
dsp2 square planar
sp3d trigonal bipyramidal
sp3d2 octahedral (outer orbital)
d2sp3 octahedral (inner orbital)

4. The empty orbitals hybridized before participation in bonding and the type of hybridisation
depends on the nature of metal and nature of ligands.

5. Under the influence of strong field ligands, the inner shell d orbitals are involved in
hybridization to form inner orbital or low-spin or spin-paired complexes (with (n-1)d, ns and
np orbitals). But, when the approaching ligands are relatively weak, the metal utilises its outer
d- orbitals to give outer orbital or high-spin or spin-free complexes (with ns, np and nd orbitals).

6. The inner orbital complexes with no unpaired electrons are diamagnetic and outer orbital
complexes with unpaired electrons are paramagnetic in nature.

Inner orbital Complex

Consider [Co(NH3)6]3+.
In this central metal atom Co atomic no. is 27. The electronic configuration of Co =
(Ar)183d74s2
Co3+=(Ar)183d6

There is involvement of two 3d, one 4s and three 4p orbitals in hybridization. So, electrons are
arranged in d2sp3 hybrid orbitals by pairing up of electrons in first three d orbitals. All six
hybrid orbitals are made vacant, and each of them accepts a pair of electrons from ligand
molecule. There are no unpaired electrons. So, the complex is diamagnetic.

Consider [Ni(CN)4]2-
All electrons are paired so complex will be diamagnetic in nature.

Outer Orbital Complex

Consider [CoF6]3-
In this central metal atom Co atomic no. is 27. The electronic configuration of Co =
(Ar)183d74s2
Co3+=(Ar)183d6

There is involvement of one 4s, three 4p and two 4d orbitals in hybridization. So, electrons are
arranged in sp3 d2 hybrid orbitals. All six hybrid orbitals are vacant, and each of them accepts
a pair of electrons from ligand molecule. There are three unpaired electrons in 3d orbitals. So,
the complex is highly paramagnetic.
Consider [CoCI4]–

Since, complex has unpaired electrons, it is paramagnetic in nature.

Limitations of VBT of complexes

1. This theory can explain the quantisation of the magnetic moment.

2. It doesn’t explain existence of inner orbital and outer orbital complexes with the same
ligands in different conditions.

3.It doesn’t explain the origin of colour of complexes.

IUPAC Nomenclature of Coordination Compounds

A. To name a coordination compound, no matter whether the complex ion is the

cation or the anion, always name the cation before the anion. (This is just like
naming an ionic compound.)

B. In naming the complex ion:

1. Name the ligands first, in alphabetical order, then the metal

atom or ion. Note: The metal atom or ion is
written before the ligands in the chemical formula.

2. The names of some common ligands are listed in Table 1.

� For anionic ligands end in "-o"; for anions that end in "-
ide"(e.g. chloride), "-ate" (e.g. sulfate, nitrate), and "-ite" (e.g.
nirite), change the endings as follows: -ide -o; -ate -
ato; -ite -ito

� For neutral ligands, the common name of the molecule is

used e.g. H2NCH2CH2NH2 (ethylenediamine). Important
exceptions: water is called ‘aqua’, ammonia is called
‘ammine’, carbon monoxide is called ‘carbonyl’, and the
N2 and O2 are called ‘dinitrogen’ and ‘dioxygen’.

Table 1. Names of Some Common Ligands

Anionic Names Neutral Ligands Names

Ligands

Br- Bromo NH3 ammine

 F- Fluoro H2O aqua

O2- Oxo NO Nitrosyl

OH- Hydroxo CO Carbonyl

CN- Cyano O2 dioxygen

C2O42- Oxalate N2 dinitrogen

CO32- Carbonato C5H5N pyridine

CH3COO- Acetate H2NCH2CH2NH2 ethylenediamine

3. Greek prefixes are used to designate the number of each type of ligand in the
complex ion, e.g. di-, tri- and tetra-. If the ligand already contains a Greek prefix
(e.g. ethylenediamine) or if it is polydentate ligands (ie. can attach at more than
one binding site) the prefixes bis-, tris-, tetrakis-, pentakis-, are used instead. (See
examples 3 and 4.) The numerical prefixes are listed in Table 2.

Table 2. Numerical Prefixes

Number Prefix Number Prefix Number Prefix

1 Mono 5 penta 9 nona (ennea)

(pentakis)

2 di (bis) 6 hexa 10 deca

(hexakis)

3 tri (tris) 7 hepta 11 undeca

 4 tetra 8 octa 12 dodeca
(tetrakis)

4. After naming the ligands, name the central metal. If the complex ion is a cation,
the metal is named same as the element. For example, Co in a complex cation is
call cobalt and Pt is called platinum. (See examples 1-4). If the complex ion is an
anion, the name of the metal ends with the suffix –ate. (See examples 5 and 6.).
For example, Co in a complex anion is called cobaltate and Pt is called platinate.
For some metals, the Latin names are used in the complex anions e.g. Fe is called
ferrate (not ironate).

Table 3: Name of Metals in Anionic Complexes

Name of Metal Name in an Anionic Complex

Iron Ferrate

Copper Cuprate

Lead Plumbate

Silver Argenate

Gold Aurate

Tin Stannate

5. Following the name of the metal, the oxidation state of the metal in the complex
is given as a Roman numeral in parentheses.
C. To name a neutral complex molecule, follow the rules of naming a complex
cation. Remember: Name the (possibly complex) cation BEFORE the (possibly
complex) anion.See examples 7 and 8.

1. [Cr(NH3)3(H2O)3]Cl3

Answer: triamminetriaquachromium(III) chloride

Solution: The complex ion is inside the parentheses, which is a cation.

The ammine ligands are named before the aqua ligands according to
alphabetical order.

Since there are three chlorides binding with the complex ion, the
charge on the complex ion must be +3 (since the compound is
electrically neutral).

From the charge on the complex ion and the charge on the ligands, we
can calculate the oxidation number of the metal. In this example, all
the ligands are neutral molecules. Therefore, the oxidation number of
chromium must be same as the charge of the complex ion, +3.

2. [Pt(NH3)5Cl]Br3

Answer: pentaamminechloroplatinum(IV) bromide

Solution: The complex ion is a cation, the counter anion is the 3

bromides.

The charge of the complex ion must be +3 since it bonds with 3

bromides.
 The NH3 are neutral molecules while the chloride carries - 1 charge.
Therefore, the oxidation number of platinum must be +4.

3. [Pt(H2NCH2CH2NH2)2Cl2]Cl2

Answer: dichlorobis(ethylenediamine)platinum(IV) chloride

Solution: ethylenediamine is a bidentate ligand, the bis- prefix is used instead

of di-

4. [Co(H2NCH2CH2NH2)3]2(SO4)3

Answer: tris(ethylenediamine)cobalt(III) sulfate

Solution: The sulfate is the counter anion in this molecule. Since it takes 3
sulfates to bond with two complex cations, the charge on each complex cation
must be +3.

Since ethylenediamine is a neutral molecule, the oxidation number of cobalt

in the complex ion must be +3.

Again, remember that you never have to indicate the number of cations and
anions in the name of an ionic compound.

5. K4[Fe(CN)6]

Answer: potassium hexacyanoferrate(II)

Solution: potassium is the cation and the complex ion is the anion.

Since there are 4 K+ binding with a complex ion, the charge on the complex
ion must be - 4.

Since each ligand carries –1 charge, the oxidation number of Fe must be +2.
The common name of this compound is potassium ferrocyanide.

6. Na2[NiCl4]

Answer: sodium tetrachloronickelate(II)

Solution: The complex ion is the anion so we have to add the suffix –ate in
the name of the metal.

7. Pt(NH3)2Cl4

Answer: diamminetetrachloroplatinum(IV)

Solution: This is a neutral molecule because the charge on Pt+4 equals the
negative charges on the four chloro ligands.

If the compound is [Pt(NH3)2Cl2]Cl2, eventhough the number of ions and

atoms in the molecule are identical to the example, it should be named:
diamminedichloroplatinum(II) chloride, a big difference.

8. Fe(CO)5

Answer: pentacarbonyliron(0)

Solution: Since it is a neutral complex, it is named in the same way as a

complex cation. The common name of this compound, iron carbonyl, is used
more often.

9. (NH4)2[Ni(C2O4)2(H2O)2]

Answer: ammonium diaquabis(oxalato)nickelate(II)

Solution: The oxalate ion is a bidentate ligand.

10. [Ag(NH3)2][Ag(CN)2]
Answer: diamminesilver(I) dicyanoargentate(I)

You can have a compound where both the cation and the anion are complex
ions. Notice how the name of the metal differs even though they are the same
metal ions.

Give the molecular formula of the following coordination compounds.

1. hexaammineiron(III) nitrate

2. ammonium tetrachlorocuprate(II)

3. sodium monochloropentacyanoferrate(III)

4. potassium hexafluorocobaltate(III)

Answers:

1. [Fe(NH3)6](NO3)3

2. (NH4)2[CuCl4]

3. Na3[FeCl1(CN)5]

4. K3[CoF6]

Give IUPAC name of the following coordination compounds.

1. [CoBr(NH3)5]SO4

2. [Fe(NH3)6][Cr(CN)6]

3. [Co(SO4)(NH3)5]+
4. [Fe(OH)(H2O)5]2+

Answers:

1. Pentaamminebromocobalt(III) sulfate

2. Hexaammineiron(III) hexacyanochromate (III)

3. Pentaamminesulfatocobalt(III) ion

4. Pentaaquahydroxoiron(III) ion