Transitions Metals: The elements belongs to d-block and their atoms and

simple ions contains vacant d-orbitals are called transition elements. The
transition elements are placed in between s- and p- block elements in periodic
table hence they have got their name as transition elements. The general
valence shell electronic configuration of these elements is (n-1)d 1-10ns1-2.There
are four transition element series in periodic table on the basis of partially
filled d-orbitals.
i) First or 3d transition series: 10 elements from Sc (21) to Zn (30) with
valence shell electronic configuration 3d1-104s2.
ii) Second or 4d transition series: 10 elements from Y (39) to Cd (48)
with valence shell electronic configuration 4d1-105s2.
iii) Third or 5d transition series: Elements from La (57) to Hf (72) to Hg
(80) with valence shell electronic configuration 5d 1-106s2.
iv) Fourth or 6d transition series: Elements from Ac (89), Rf(104) to Uub
(112) with valence shell electronic configuration 6d 1-107s2.
These transition elements belong to group 3 to 12 in periodic table.
Non-Typical transition elements:
Those transition elements whose d-orbitals are completely filled (d 10)
and can not exhibit the characteristic properties of typical transition
elements are called non-typical transition elements. for eg: Zn,Cd,&Hg.
Their general valence shell electronic configuration is represented as (n-
1)d10, ns2. General properties of non-typical transition elements are:
i. Fixed oxidation state
ii. Compounds are colorless. For example: ZnO, ZnCO3, ZnSO4.7H2O,
etc.
iii. Do not show the catalytic property.
iv. Relatively low melting and boiling point.
v. Completely filled d-sub shell.
Characteristics of Transition Elements: The following are the
common characteristics of transition elements.
1. Their general valence shell electronic configuration is (n-1)d 1-10 ns1-2
(where (n-1)d subshell is partially filled).
2. The cation of transition elements have a great tendency to form
complexes with other molecules or ions called ligands.
3. Most of the d-block metal compounds are colored in solid or in
solution state however the compounds of some metal ions of
transition elements are colorless like-Sc3+, Ti4+, Cu+, Ag+, Zn++.
4. Most of the transition elements show paramagnetic behaviour due to
unpaired d-electrons (exceptions are Sc3+, Ti4+, Cu+, etc.) are
diamagnetic which do not have unpaired d-electrons. The presence of
unpaired electrons causes these elements behave like a permanent
magnet. It is very interesting to note that paramagnetic substance
show increase in weight in magnetic field but diamagnetic substance
show decrease in weight.
Total magnetic moment (Ƞm) of cation = BM where n = number of
unpaired electron.
5. The transition metals are lustrous (shining) when pure. They are hard
with high densities. Their melting and boiling point are very high. This is
due to the metallic bond.
6. They are good thermal and electrical conductions. This is due to
presence of ‘free’ electrons in solid metal.
7. They have high tensile strength, malleability and ductility. These
properties are also the consequences of metallic bonding.
8. They form alloys among themselves as well as with non-transition
metals.
9. They exhibit variable oxidation states (variable valencies) in their
compounds.
10. Many transition metals and their alloys and their compounds have
good catalytic activities. They are efficient catalyst.
11. Some of transition metals are biologically important and catalyze
biochemical reaction: for example iron, cobalt, copper, molybdenum and
Oxidation states of Transition metal:
One of the most important features of the transition element is that they
exhibit variable oxidation states in their compounds which are related to
their electronic configuration. Reasons for variable oxidation states are:
• Variable oxidation states of these elements are due to involvement of
outer ns orbitals and inner (n-1)d orbital electrons in bonding as the
energy of ns and (n-1)d subshell are nearly equal.
• Oxidation states increase on moving down the group. Iron shows +2
and +3 oxidation states but the highest oxidation state of 8 is shown
by Ruthenium (Ru) and Osmium (Os).
• Transition metals also form compounds in low oxidation state such as
+1 and zero. For example: in nickel tetra carbonyl [Ni(CO) 4], Ni has
zero oxidation state.
• Transition elements in +2 and +3 oxidation states are mostly ionic
bonds but for higher oxidation states, compounds are covalent. For
example, Permagnate, MnO4-, where all the bonds between
manganese and oxygen are covalent.
Complex ions and metal complexes:
A compound in which metal atom or metal ion is co-ordinated into two
or more ligands is called metal complexed or co-ordination compound.
The transition metal atom or the cations derived from them have a great
tendency to form complex compounds with certain molecules (e.g. CO,
NO, NH3, etc.) or ions (e.g. F-, Cl-, CN-,etc.) These molecules or ions
attaching the metal atom or metal ion are called ligands. These ligands
contains contain one or more lone pairs of electrons which they can
easily donate to the transition metal atom or cation and thus complete the
vacant orbitals of those metal atoms or cations through the formation of
L→M co-ordinate bonds. The great tendency of the transition metal
atom or cation to form the complex compound is due to the following
properties.
• Due to small size of the transition metal atom or their cations and high
effective nuclear charge. They may have high positive charge density
on them
The high positive charge density makes the transition metal atom or cation
to accept lone pairs of electron from the ligands.
• The transition metal atoms or ions have small size with high positive
charge density. Such species can attract lone pairs from ligands.
• They are capable of forming stable complexes with several oxidation
states.
• Transition metals/ions with vacant (n-1)d-orbitals of appreciate energies
can form ligands to metal (L→M) co-ordinate covalent bond resulting
co-ordination complexes/Lewis acid-base complexes.
Eg. Fe++ + 6 CN- ↔[Fe(CN)6]4+
Co3+ + 6NH3 ↔ [Co(NH3)6]3+
Cu++ + 4 NH3 ↔[Cu(NH3)4]++
Factors affecting the formation of metal complexes
i. The metal ion should be small size.
i. It should have a high positive charge.
ii. It should have vacant low energy orbital to accept lone pairs of
Different terms used in metal complexes
a. Ligands or Co-ordinating groups: Any atom, ion or neutral species capable
of donating lone pairs of electrons and attached directly to the central metal
atom or ion during the formation of complex compound are called ligands.
The ligands are attached to the central metal atom or ion through co-ordinate
bonds. The ligands which can donate one, two, or more lone pairs are called
unidentate, bidentate and multidentate ligands respectively. F-, Cl-, Br-, NH3,
H2O are unidentate ligands. H2N-CH2-CH2-NH2 ethylene diammine is
bidentate.
b. Central Ion, Centre for co-ordination: The central transition metal ions
having vacant d-orbitals in which neutral molecules or anions are attached is
called centre for co-ordination. For example, in [Cu(NH3)4]SO4, Cu is a centre
for co-ordination.
c. Co-ordination Number: Total number of ligands attached to central metal
ion is called co-ordination number. For example, in [Ag(NH3)2]+ co-ordination
number is two.
d. Co-ordination sphere and ionizable sphere: The central metal atom and
ligands are directly attached to it are called as co-ordination sphere. It is
written within square bracket. The co-ordination sphere behaves as single
++
Shapes of complex Ions: Transition metals can have any four possible
ion complex shapes. i.e., Linear, Square planar, Tetrahedral and
Octahedral. Tetrahedral and Octahedral complexes are most common.
The ion complex shape is orientation of ligands or molecules that are
attached to the transition metal. The shape that metal takes depends on
the co-ordination number (number of ligands) and how large ligands are.
The possible shapes are as follows:

Co-ordination 2 4 4 6
number

Shape Linear Tetrahedral Square planar Octahedral

Bond Angle 180˚ 109.5˚ 90˚ 90˚

Occurrence Ag+ Complexes Large ligands(Cl-) Pt2+ complexes Commonest

Examples [Ag(NH3)2]+ [CuCl4]2- [PtCl4]2- [Cu(H2O)6]2+

i) Linear (two ligands attached and linear shape): The most
commonly used linear complex occurs in Tollens’ reagent. E.g.,
H3N-Ag-NH3.
ii) Square planar (four ligands are attached and square planner
shape): There are two ligands pointing up and two ligands pointing
down; none are pointing to the sides. The most common square
planner complexes occur with platinum (II) metals. Cisplatin is a
neutral complex, [Pt(NH3)2]Cl2. But they are also found with
rhodium (I), palladium (II), and gold (III).
iii) Tetrahedral (four ligands attached and square planar shape): It
has one ligand pointing up and one pointing down and two are pointing
front and back. Two very similar ions crop up commonly at this level:
[CuCl4]2- and [CoCl4]2-. The copper(II) and cobalt(II) ions have four
chloride ions bonded to them rather than six because the chloride ions
are too big to fit any more around the central metal ion.
iv) Octahedral complex (six ligands attached and octahedral shape):
These complex ions are those species in which the central metal ion is
forming six bonds or attached to six ligands. These ions have an
octahedral shape. Four of the ligands are in one plane, with the fifth on
above the plane, and the sixth one below the plane. The diagram shows
four fairly random examples of octahedral ions. Hexaamminecobalt(III)
chloride is the chemical compound with the formula [Co(NH3)6]Cl3.
Hexaaquacopper(II) ion has formula [Cu(H2O)6]2+.
A. Octahedral complexes: These type of complexes are formed either
by d2sp3(inner orbital) or sp3d2 (outer orbital) hybridization.
i. Inner orbital complexes [Cr(NH3)6]3+
Electronic configuration of Cr3+ is [Ar]3d34s04p0
The two 3d, one 4s and three 4p-orbitals (all of nearly equal energy)
hybridize to give d2sp3 hybrid orbitals and shape will be octahedral.
Therefore [Cr(NH3)6]3+ has octahedral geometry.

Other examples of octahedral inner complexes are [Fe(CN) 6]4-

3-
 Difference between strong and weak field ligand

Strong field ligand Weak field ligand

• ligand which produce strong field • Ligand which produce weak field
are known as strong field ligand are known as weak field ligand
• They cause splitting of d-orbitals • They cause splitting of d-orbitals to
to a larger extent a smaller extent
• In a strong field 10Dq is usually • In a weak field 10Dq is usually less
more • As energy gap 10Dq is less
• As energy gap 10Dq is more electrons remain unpaired
electrons generally pair up • As electrons remain unpaired they
• As electron pair up they give rise give rise to high spin complexes
to low spin complexes • Complexes are mostly
• Complexes are mostly diamagnetic paramagnetic in nature
or weak paramagnetic in nature.
Color of Transition metal compounds:
Many of the ionic and covalent compounds of the transition metals are
colored either in crystalline solid or solution form while that of the s- and
p- block elements are colorless. Transition metals are responsible to give
color to them.
Metal ions/species Color observed
Cu++ Blue
Cr+++ Green
MnO4- Pink
Fe++ Light green
Cr2O7- - Orange

The color of the transition metal complex is due to incompletely filled d-

orbitals and d-d electronic transition based on the crystal field splitting
theory. According to this theory, in a free isolated gaseous ion, the five d-
orbitals are degenerate (have equal energy) but in the solution or
compound state, the energy of the d-orbital is changed cause splitting into
different energy d-orbitals (t2g and eg).This is called crystal field splitting.
The energy difference between split-up orbitals (t2g and eg) lies in the
visible region. Now the electronic transition between low energy d to
high energy d-orbitals of the same subshell is called d-d transition (t 2g ↔
eg) is possible by absorption of visible radiation. Here the transition
complex absorbs the energy of definite wavelength from the surrounding
light and transmits the complementary color to the human eyes in the
visible region. Suppose that the energy gap in the d-orbitals of the
complex ion corresponds to the energy of yellow light would be
observed and its energy promotes the electron and leaves the
complementary color i.e., dark blue color is observed. This is reason why
the solution or complexes of transition metal ions are usually colorful.
Since s and p- orbitals are symmetrical geometry and their splitting does
not occur, hence their compounds are colorless. The ions having d0 or d10
configuration do not show orbital splitting, hence they are colorless.
The colour of transition metal complexes or compounds may be
explained on the basis of