Unit 5.

2 TRANSITION METAL
Transition metal is "an element whose atom has a partially filled d sub-shell,
or which can give rise to cations with an incomplete d sub-shell".
Many scientists describe a "transition metal" as any element in the d-block of
the periodic table, which includes groups 3 to 12
Zinc, cadmium, and mercury are generally excluded from the transition
metals[5] as they have the electronic configuration [ ]d10s2, with no
incomplete d shell.[13

Periodic Table

The electronic structures of the d block elements shown are:

Sc

[Ar] 3d14s2

Ti

[Ar] 3d24s2

[Ar] 3d34s2

Cr

[Ar] 3d54s1

Mn

[Ar] 3d54s2

Fe

[Ar] 3d64s2

Co

[Ar] 3d74s2

Ni

[Ar] 3d84s2

Cu

[Ar] 3d104s1

Zn

[Ar] 3d104s2

Standard Ionisation energies (IEo)

First IE-Minimum energy required to remove 1 mole of electron from
1 mole of gaseous atom at 1 atm and 298 k
Mg(g)
Mg+(g) + e
IE 1o=+740 kJmol-1
Second IE- minimum energy required to renove 1 mole of electron

from every unipositive gaseous ion at 1 atm and 298K.

Mg+(g)
Mg2+(g) + e
IE 2o = 1400 kJmol-1

 Cr(g)
Cr+ (g)
Mn(g)
Mn+(g)

Cr+ (g) + e
Cr2+(g) + e
Mn+(g)
+ e
Mn2+(g) + e

IE 1 =+ 653 kJmol-1
IE2 = + 1592 kJmol-1
IE1= +717 kJmol-1
IE 2= + 1509 kJmol-1

Characteristic properties

the formation of compounds whose colour is due to dd electronic

transitions
the formation of compounds in many oxidation states, due to the
relatively low energy gap between different possible oxidation
states[17]
the formation of many paramagnetic compounds due to the presence
of unpaired d electrons. A few compounds of main group elements
are also paramagnetic (e.g. nitric oxide, oxygen)
Hard metal with high melting and boiling point
Show catalytic activity

Variable oxidation state (number)

When a metal forms an ionic compound, the formula of
the compound produced depends on the energetics of the
process. On the whole, the compound formed is the one
in which most energy is released. The more energy
released, the more stable the compound.
The more highly charged the ion, the more electrons you
have to remove and the more ionisation energy you will
have to provide.
Manganese
Manganese has a very wide range of oxidation states in its compounds. For example:

+2

in Mn2+

+3

in Mn2O3

+4

in MnO2

+6

in MnO42-

+7

in MnO4-

Note that the charge on the complex is always the sum of the charges on the ions or
molecules that form the complex

Cu2+ + 4 NH3
Pb2+ + 2 OAcFe2+ + 6 CN-

Cu(NH3)42+
Pb(OAc)2
Fe(CN)64-

1. What is the ox. no. of the central metal in [ Rh(NH 3)5Cl](NO3)2

2, What is the charge of the complex formed by a platinum(II) metal ion surrounded by
two ammonia molecules and two bromide ion?

Naming the complex

ligand

coded by

(old name)

H2O

aqua

aquo

NH3

ammine

ammino

OH-

hydroxo

hydroxy

Cl-

chloro

F-

fluoro

CN-

cyano

no of ligands

coded by

di

tri

tetra

penta

hexa

metal

changed to

cobalt

cobaltate

aluminium

aluminate

chromium

chromate

vanadium

vanadate

copper

cuprate

iron

ferrate

 [CuCl4]2- - tetrachlorocuprate(II) ion.

[Al(H2O)2(OH)4]- - diaquatetrahydroxoaluminate ion.
[Cu(H2O)6]2+ - hexaaquacopper(II) ion.
With more than one type of ligand in an ion, the ligands are named in
alphabetical order - ignoring the prefixes. For example:
[Cu(NH3)4(H2O)2]2+ - tetraamminediaquacopper(II) ion.
Ex.1. A complex ion contains a chromium(III) bound to four water
molecules and two chloride ions.What is it formula and name?

2. Name this compound : K4[Ni(CN)4], [Mo(NH3)3Br3]NO3

3. Write the formula for sodium diaquadioxalatoruthenate(III)

The formation of coloured compounds

Complex ions containing transition metals are

usually coloured, whereas the similar ions
from non-transition metals aren't. That
suggests that the partly filled d orbitals must
be involved in generating the colour in some
way. Remember that transition metals are
defined as having partly filled d orbitals

Fe

[Ar] 3d64s2

Fe2+

[Ar] 3d6

Fe3+

[Ar] 3d5

The formation of complex ions

What is a complex ion?
A complex ion has a metal ion at its centre with a number of other molecules or ions surrounding
it. These can be considered to be attached to the central ion by co-ordinate (dative covalent)
bonds. (In some cases, the bonding is actually more complicated than that.)
The molecules or ions surrounding the central metal ion are called ligands.
Simple ligands include water, ammonia and chloride ions.

[Fe(H2O)6]2+
[Co(NH3)6]2+
[Cr(OH)6]3[CuCl4]2-

Any ion or molecule with a pair of nonbonding electrons can be a ligand. Many ligands are
described as monodentate(literally, "one-toothed") because they "bite" the metal in only
one place. Typical monodentate ligands are given in the figure below.

Ethylenediamine (en) is a typical bidentate ligand.

Ethylenediamine is also an example of a chelating ligand. The term chelate comes

from a Greek stem meaning "claw." It is used to describe ligands that can grab the
metal in two or more places, the way a claw would.

Coordination Numbers
Transition-metal complexes have been characterized with
coordination numbers that range from 1 to 12, but the most
common coordination numbers are 2, 4, and 6. Examples of
complexes with these coordination numbers are given in the
table below.

Metal Ion

Ligand

Complex

Coordination
Number

Ag+

2 NH3

Ag(NH3 )2 +

Ag+

2 S2 O3 2-

AgCl2 -

Ag+

2 Cl-

Ag(S2O3)23-

Pb 2+

2 OAc-

Pb(OAc)2

Cu +

2 NH3

Cu(NH3 )2 +

Cu 2+

4 NH3

Cu(NH3)42+

Zn 2+

4 CN-

Zn(CN)4 2-

Hg2+

4 I-

HgI 4 2-

Co 2+

4 SCN-

Co(SCN)42-

Fe2+

6 H2 O

Fe(H2 O)6 2+

Fe3+

6 H2 O

Fe(H2 O)6 3+

Fe2+

6 CN-

Fe(CN)64-

Co 3+

6 NH3

Co(NH3)63+

Ni2+

6 NH3

Ni(NH3 )6 2+

The geometry of the complex ions

6-co-ordinated complex ions

4-co-ordinated complex ions

Tetrahedral ions

A square planar complex

Oxidation numbers of vanadium

Oxidation State

Ion

Color

+5

VO3- or VO2+

Yellow

+4

VO2+

Blue

+3

V3+

Green

+2

V2+

Violet

Explaining the changes in terms of redox potentials (electrode potentials)

Using zinc as the reducing agent
The first stage of the series of reductions
Let's look at the first stage of the reduction - from VO2+ to VO2+. The redox potential for the vanadium halfreaction is given by:

The simple principle is that if you couple two of these half-reactions together, the one with the more
positive E value will move to the right; the one with the more negative (or less positive) E moves to
the left.

Stability of the oxidation numbers

How to determine the relative stability of the different oxidation
numbers?
Mn more stable +2 than +3
Fe more stable +3 than +2
Look at the arrangement of the electron in the d orbital

Copper (I)
The disproportionation of copper(I) ions in solution
Copper(I) chemistry is limited by a reaction which occurs involving simple
copper(I) ions in solution. This is a good example of disproportionation - a
reaction in which something oxidises and reduces itself. Copper(I) ions in
solution disproportionate to give copper(II) ions and a precipitate of copper.
The reaction is:

Any attempt to produce a simple copper(I) compound in solution results in this happening. For example, if you react copper(I)
oxide with hot dilute sulfuric acid, you might expect to get a solution of copper(I) sulfate and water produced. In fact you get a
brown precipitate of copper and a blue solution of copper(II) sulfate because of the disproportionation reaction.
Cu2O +

H2SO4

Cu

CuSO4 +

H2O

Stabilizing the copper(I) oxidation state

Insoluble copper(I) compounds
We've already seen that copper(I) iodide is produced as an off-white
precipitate if you add potassium iodide solution to a solution containing
copper(II) ions. The copper(I) iodide is virtually insoluble in water, and so
the disproportionation reaction does not happen.
Similarly copper(I) chloride can be produced as a white precipitate
(reaction described below). Provided this is separated from the solution
and dried as quickly as possible, it remains white. In contact with water,
though, it slowly turns blue as copper(II) ions are formed. The
disproportionation reaction only occurs with simple copper(I) ions in
solution.

Copper(I) complexes
Forming copper(I) complexes (other than the one with water as a ligand) also stabilizes the copper(I)
oxidation state. For example, both [Cu(NH3)2]+ and [CuCl2]- are copper(I) complexes which do
not disproportionate. The chlorine-containing complex is formed if copper(I) oxide is dissolved in concentrated
hydrochloric acid. You can think of this happening in two stages. First, you get copper(I) chloride formed:
Cu2O(s) + 2HCl(aq)

2CuCl(s) +

H2O(l)

But in the presence of excess chloride ions from the HCl, this reacts to give a stable, soluble copper(I)
complex.
CuCl(s) +

Cl(aq)

[CuCl2](aq)

You can get the white precipitate of copper(I) chloride (mentioned above) by adding water to this solution.
This reverses the last reaction by stripping off the extra chloride ion.

The chemistry of copper

Reactions of hexaaquacopper(II) ions with ammonia solution

The ammonia acts as both a base and a ligand. With a small amount of ammonia, hydrogen ions are pulled off the hexaaqua ion exactly as in the
hydroxide ion case to give the same neutral complex.
[Cu(H2O)6]2+
[Cu(H2O)6]2+

+
+

2NH3

[Cu(H2O)4(OH)2]

+ 2NH4+

2NH3

[Cu(H2O)4(OH)2 ]

2NH4+

That precipitate dissolves if you add an excess of ammonia. The ammonia replaces water as a ligand to give tetraamminediaquacopper(II) ions.
Notice that only 4 of the 6 water molecules are replaced.
[Cu(H2O)6]2+

4NH3

[Cu(NH3)4(H2O)2 ]2+

H2O

Chemistry of chromium
Electron configuration [Ar] 3d5 4s1

Table 1: Chromium is found in many different compounds, all with different uses and properties.
Oxidation State

Compounds

-2

Na2[Cr(CO)5]Na2[Cr(CO)5]

-1

Na2[Cr(CO)10]Na2[Cr(CO)10]

0
+1
+2

Cr(CO)6Cr(CO)6
CrOCrO, CrF2CrF2, CrCl2CrCl2, CrSCrS, Cr2(SO4)3Cr2(SO4)3

+3

Cr2O3Cr2O3, CrF3CrF3, CrCl3CrCl3, [Cr(H2O)6]3+[Cr(H2O)6]3+

+4
+5
+6

CrO2CrO2, CrF4CrF4
CrF5CrF5
CrO3CrO3, Na2Cr2O7Na2Cr2O7, CrO24CrO42, CrOF4CrOF4

Reactions of chromium(III) ions in solution

The simplest ion that chromium forms in solution is the hexaaquachromium(III) ion [Cr(H2O)6]3+.

Complementary colours

 Ex.1. The complex ion [Co(NH3)4Cl2]+ absorbs light primarily in the

red region of the visible spectrum (680 nm) What is the color of the
complex?
2. The [Cr(H2O)6]2+ ion has an absorption band at about
630nm.Which of the following colors sky blue,yellow ,green or deep
red is most likely to describe this ion?

CRYSTAL FIELD THEORY

Explain the bonding in complex ions in terms of electrostatic force.
Two types of electrostatic interaction-i) between +ve metal ion & vely charged ligand .ii)electrostatic repulsion between the lone pairs
on the ligands and the e- in the d orbitals of the metal.
-

The diagram shows the arrangement of the d electrons in a

Cu2+ion before and after six water molecules bond with it.

-crystal field splitting is the energy different between two sets of d orbitals in a
metal atom when ligands are present

 -the magnitude of
depend on the metal and the nature of the
ligands; it has direct effect on the color and magnetic properties of
complex ion.

The factors affecting the colour of a transition

metal complex ion
The nature of the ligand
Different ligands have different effects on the energies of the d
orbitals of the central ion. Some ligands have strong electrical fields
which cause a large energy gap when the d orbitals split into two
groups. Others have much weaker fields producing much smaller
gaps.

Magnetism
The magnitude of crystal splitting determine the magnetic properties
of a complex ion.
Many complex exhibit simple paramagnetism.
[Ti(H2O)6]3+ having 1 d electron.is always paramagnetic
[Co(CN)6]3- have no unpaired e [CoF6]3- have 4 unpaired e-