TRANSITION ELEMENT

1. GENERAL PROPERTIES
1.1 . Physical properties
a. Hard
b. High density
c. High melting point

1.2. Chemical properties

a. Exhibit variable oxidation states in their compounds
b. Form complexs
c. From colored compounds
d. Show catalytic properties

2. VARIABLE OXIDATION STATES

The following table shows the relative stability of oxidation state of d - block metal ions.

Sc +3
[Ar]3d14S2 (Ar)
Ti +2 +3 +4
[Ar]3d24S2 (Ar)
V +2 +3 +4 +5
[Ar]3d34S2 (Ar)3d2 (Ar)
Cr +2 +3 +4 +5 +6
5
[Ar]3d 4S 1 (Ar)3d3 [Ar]
Mn +2 +3 +4 +5 +6 +7
5 2
[Ar]3d 4S (Ar)3d5 (Ar)3d3 (Ar)
Fe +2 +3 +4 +5 +6
6 2
[Ar]3d 4S (Ar)3d6 (Ar)3d5
Co +2 +3 +4 +5
7 2
[Ar]3d 4S (Ar)3d7 (Ar)3d6
Ni +2 +3 +4
8 2
[Ar]3d 4S (Ar)3d8 (Ar)3d6
Cu +1 +2
10 1
[Ar]3d 4S (Ar)3d 10 (Ar)3d9
Zn +2
10 2
[Ar]3d 4S (Ar)3d10

The number of oxidation state increases from Sc (one oxidation state) to Mn (seven oxidation
states) and then it decreases from Mn (seven oxidation states) to Zn (one oxidation state).

The electrons in 3d and 4s orbitals are valence electrons. The 4s orbital has slightly higher
energy than the 3d orbitals. During ionization, electrons are removed from 4s orbital first
followed by the electrons from 3d orbitals.
Ion with lower oxidation state is formed when electrons are removed from the 4s orbital.
Example:
Fe2+ = [Ar]3d6
Ion with higher oxidation state is form by further removal of electrons from than 3d orbitals.

Example:
Fe3+ = [Ar]3d5

Oxidation states that are more stable are marked bold.

Electronic configuration of ion contributes to the stability of the ion. Usually ion with half-filled
3d orbitals or fully-filled is stable or ion ioelectronics with Argon is stable.
From Sc to Mn:
‘Ion’ with higher oxidation state is more stable than ‘ion’ with lower oxidation states. The ‘ion’
with the higher oxidation state is isoelectronic to argon.
Example:
‘Ti4+ ion’ is stable due to the ion is isoelectronic with the argon atom.

From Mn to Zn:
Ion with lower oxidation state is more stable than ion with higher oxidation states. The ion with
the lower oxidation state is either has its 3d orbital half-filled or retaining then higher number of
electron pair in the 3d orbital.
Examples:
Fe3+ ion is stable due to the 3d orbitals are half-filled.
Zn2+ ion is stable due to the 3d orbitals are fully-filled or maximum number of electron pairs.

‘Ion’ with the higher oxidation state usually does not exist in the form of simple ion due to the
high density of charge of the ‘ion’. Thus, it forms oxoanions and oxocompounds.
Examples:
Oxoaonios: [Ti(H2O)4O]2+,[V(H2O)4O]3+
Oxo-compounds: TiO2, V2O5, K2CrO4, K2Cr2O7, KMnO4

Ion with the lower oxidation state exists in the form of simple ionic compounds and hydrated
free ion in aqueous solutions.
Examples:
Simple ionic compound: MnCl2, FeCl3, CuSO4, Ni(NO3)2
Hydrated free ion: [Zn((H2O)6]2+ , [Cr((H2O)6]3+

‘Ion’ with the higher oxidation state is usually strong oxidizing agent than the ion at the lower
oxidation state. It is easily reduced to the ‘ion’ at the lower oxidation state.
Examples: MnO4– + 5e + 8H+ → Mn2+ + 4H2O
Fe3+ + e → Fe2+
3. FORMATION OF COMPLEX
L
Complex is compound formed when a central
atom or ion (of transition metal) is bonded to
several molecules or ions (ligands) by dative L M L
(coordinate) bond.
Ligands are molecules or ions that have at least
one non-bonding pair of electrons that are readily M = metal atom /
to
ionbe donated to the metal atom or ion to form a L
dative bond. Ligands are Lewis bases. L = ligands

3.1 Formation of complex

Atoms or ions of transition metal have exceptionally strong tendency to form complex because
of its atoms or ions have empty d orbitals in their valence shell.

In the formation of complex, metal atom / ion accept the non-bonding electron pairs from
ligands. The electron pairs are filled into the empty d orbitals of the metal atom / ion. Thus, the
metal atom or ion acts a Lewis acid.

3.2 Name and classification of ligand

A ligand is classified according to the number of donor atom per ligand or the number of dative
bond formed per ligand.
Monodentate: Form one dative bond per ligand
H2O (aqua), NH3 (ammine), CO (carbonyl)
F– (fluoro), Cl– (Chloro), Br– (Bromo), OH– (hydroxo), CN– (cyano), NO2– (nitro), SCN–
(thiocyanato)

Bidentate: Form two dative bonds per ligand

–
H2NCH2CH2NH2, CH3C – CCH3, O–C–C–O –
(ethane-1,2-diamine)
HON NOH O O
(dimethylglyoxim) (ethanedioate)

Hexadentate: Form six dative bonds per ligand

–
OOCCH2 CH2COO–
:NCH2CH2N:
–
OOCCH2 CH2COO–
(Ethylenediaminetetraacetate or EDTA)

The bidentate and hexadentate ligands are called Polydentate ligands or chelate compound or
chelate.
Chelates form ring structures that encircle and trap the central metal ion.
3.3 Names of complex

Naming a complex depends on the types of the complex. There are three types of complex,
namely neutral complex, cationic complex and anionic complex.
The charge of complex can be determined by calculating the total oxidation number of ligande
and the metal ion.
Examples: [Ni(CO)4 ]
CO molecule is neutral charge. Thus the total oxidation number is zero. Therefore, oxidation
number of nickel is zero because the complex is neutral.
[Fe(H2O)5SCN ]2+
H2O molecule is neutral charge. Thus the total oxidation number is zero. SCN has 1 negative
charge. Thus the oxidation number is –1. Therefore, the oxidation number of ferum is +3
because the total charge of complex is 2+.

Example: [Ni(C2O4)3]4–
C2O42- has total cahrge 2–. Three unit of this ion have a total charge of 6–. Therefore, the
oxidation number of nickel is +2 because the total charge of complex is 4–.

In naming a complex, ligands are name first according to the alphabetical order. Prefixes like di,
tri and tetra is added to the name of ligand according to the number of same ligand in the
complex. In case where the name of ligand already has prefix like di or tri or tetra, prefixes like
bis, tris and tetrakis are used.

Metal is named last. If:

The complex is neutral, the name of the metal remain unchanged.
The cationic complex, the name of the metal remain unchanged and followed by the oxidation
state is stated.
The anionic complex, the suffix ‘ium’ in the name of metal is dropped and is added on with ‘ate’.
Examples:
[Ni(CO)4 ]: Tetracarbonylnickel [Fe(H2O)5SCN ]2+:Pentaaquathiocynatoferum (III) ion
[CuCl4]2– : Tetrachlorocuprate(II) ion [Ni(C2O4)3]4– : tris(ethanedioate)nickelate(II) ion

4. COLOUR OF COMPLEX
Most complexes of transition metals are colored. The red
color of a complex is depends on the nature of the central
metal ion, the oxidation state of the metal ion and the type orange purple
of ligand. white
The white light is made up of three major colours, red, yellow green blue
yellow and blue. When these major colours are mixed,
they produce secondary color like green, orange and
purple.
The d orbitals in the metal atom or ion are at the same energy level.
3d

However, when ligands approach the central atom during the formation of complex, the electric
fields of the non-bonding electron pair in ligands and the electric fields of the d orbitals in the
metal ion repel against each other. This causes the d orbitals to split into 2 groups of orbitals with
different energy. This is called the d-d splitting of d orbitals.

d (x2- y2) and dz2 d-d splitting in octahedral complex is due to the
↑↓ ↑ 3dligands that approaching the central atom at the
direction along the x, y and the z exes. This pushes d
↑↓ ↑↓ ↑↓ ↑↓ ↑ E = hv 2 2 2
(x - y ) and dz orbitals to higher energy level and dxz,
dyz and dyx orbitals to lower energy level. These two
↑↓ ↑↓ ↑↓ groups of d orbitals are separated with a small energy
gap, E that corespone to a discrete wave length, v from
dxz, dyz and dyx the vivible light region.
When electron from the lower energy level absorbs v
from the visible light, it is excited and moves up the
higher energy level.
dxz, dyz and dyx The remaining wave lengths pass through and give the
colour to the complex.
↑↓ ↑↓ ↑↓
3d
↑↓ ↑↓ ↑↓ ↑↓ ↑ E = hv d-d splitting in tetrahedron complex is due to the
ligands that approaching the central atom at the
↑↓ ↑↓ direction between the x, y and the z exes. This
d (x2- y2) and dz2 pushes dxz, dyz and dyx orbitals to higher energy level
and d (x2- y2) and dz2 orbitals to lower energy level.

If d-d splitting created a bigger energy gap, the complex will absorb higher frequency from the
visible light. Thus, it gives color that corresponds to the lower frequency.
Metal ion that has higher oxidation state causes bigger energy gap during d-d splitting.

Example: [Cu(H2O)6]2+ is blue color.

During the formation of this complex, the 3d orbitals of copper (II) ion under go d-d splitting
into 2 groups of orbitals. Electron form the lower energy level moves to the higher energy level
by absorbing red and yellow frequencies from the visible light. Blue frequency passes through
and gives blue color to the solution.
d (x2- y2) and dz2
d-d splitting Blue frequency
3d absorb red and ↑↓ ↑ passes through
↑↓ ↑↓ ↑↓ ↑↓ ↑ and gives blue
yellow frequencies ↑↓ ↑↓ ↑↓ color to the
solution
dxz, dyz and dyx
5. STABILITY OF COMPLEX

Metal ion of transition metal forms hexaaqua complex, [M(H2O)6]n+ and forming an equilibrium
as the following.
Mn+(aq) + 6H2O(l) ⇌ [M(H2O)6]n+(aq)

At the equilibrium, Kstability = [M(H2O)6]n+/ [Mn+][H2O]6

Stable complex has bigger value for the stability constant, Kstability. Thus, the equilibrium is
shifted right and favors the formation of the complex ion.
When some solution contains ligand L is added into the equilibrium, the ligand, L may or may
not form complex ion with the metal ion, M by replacing H2O is depends on the relative value of
the stability constant, Kstability, of the two complexes.
If ligand, L, forms more stable complex with metal ion, molecules of ligand, L, would replace
water molecules in the [M(H2O)6]n+ complex ions to form [MLm]n+ complex ion. This would
accompanied by the change of color of the solution from color A to color B.

[M(H2O)6]n+(aq) + mL(l) ⇌ [M(L)m]n+(aq) + 6H2O(l)

Color A color B

Example: When some ammonia solution is added into aqueous solution of copper (II) sulphate,
blue precipitate is formed. If excess of ammonia solution is added, the blue precipitate dissolves
to form a dark blue solution. When some EDTA4 – solution is added, the color turns light blue
again.

The stability of complex increases according to the following order:

[Cu(H2O)6]2+ < [Cu(H2O)4(OH)2 ] < [Cu(NH3)4]2+ < [CuEDTA]2–
Light blue blue precipitate dark blue light bleu
The reactions are:
[Cu(H2O)6]2+(aq) + 2OH– (aq) ⇌ [Cu(OH)2(H2O)4](s) + 2H2O(l)
Light blue blue precipitate
[Cu(OH)2(H2O)4](s) + 4NH3(aq) ⇌ [Cu(NH3)4]2+(aq) + 4H2O(l) + 2OH– (aq)
Blue precipitate dark blue
[Cu(NH3)4]2+(aq) + EDTA4– (aq) ⇌ [CuEDTA]2– (aq) + 4NH3(aq)
Dark blue light blue

Some important notes:

Neutral complexs are solid or precipitate.
Chelates usually form more stable complexes than monodentate ligands