Metal complex formation

Metal complex formation entails the interaction of one or more ligands with a multivalent metal cation.
Ligand systems
A ligand system is any charged or uncharged polar entity or atomic component of a substituted group
containing an excess electron or electron pair.
The nature of the bond between the ligand and the metal atom depends on the ligand acting as an electron
pair donor and the metal as an electron pair acceptor.the donation of an electron pair from ligand atom to
metal give rise to a covalent or sigma bond,in molecular orbital terminology.
In the synthesis of metal-complex dyes the organic ligand may form part of either a base or an acidic functional
group.
A basic ligand carries a lone pair of electrons that may interact with the metal ion.examples include
NH2(amino),=NH(imino),=N-(in azo or azomethine),=O(in carbonyl) or S-(in thioether).
NH
N
N
N
N
NH
M

M = Co, Ni or Cu
An acidic ligand such as OH(from carboxylic,phenolic or enolic groups),-SH(from thiophenolic or
thioenolic groups) or NH-(from amino or imino groups) loses a proton during metallisation to give a formal
negative charge.
N N HO
3
S
O
2
N
O
M
O
H
CH
3
OH (Ligand)

M = Cu,Co etc
Unidentate ligand system
A ligand molecule such as ammonia or water only one pair of electrons is utilized in forming a
coordination sigma bond with the metal. ligand system of this type are said to be unidentate and are
found in many metal-complex dye structures, satisfying sites around the central metal atom not
already sterically occupied by coordinated dye ligands.
Bidentate ligand system
Bidentate ligand system form two coordinated or covalent bonds with the central atom.when two
groups originating in the same bidentate molecule combine with the same metal ion.
M
X X
X
X
M
X
X
X
X
L
L

M
X
X
X
X
X
X

A heteroatomic ring is formed.ring formation between the metal M and salicylic acid residue (in a
dye structure) containing two donor groups is shown
Ar
N
N
O
O
O
M


N N
N N
Cl
M
+
NH
NH
nH2O

M
+
=Co,Cu,Mn,Ni,Zn
In a bidentate ligand system,there molecules of a dye containing either a terminal salicylic acid unit
or an o-nitrosonaphthol residue are able to chelate imultaneously with a trivalent metal ion of
coordination number 6,such as chromium (III) or iron (III) to form a 1:3 metal-dye complex.
O H
2
O H
2
O
2
N
COOH
N
O
Ni
+
N

Bidentate attachment of nickel atom
Such 1:2 complexes containing divalent cobalt,nickel or copper were synthesised from o-substituted
azobenzenes.
N
X
X
M
N
N
N

M=Co,Ni or Cu
X= O,NH
The copper(II) ion and formation of a bidentate 1:2 complex.
Tridentate ligand systems
Tridentate ligand system from three coordinated or covalent bonds with the central atom.the tridentate azo
systems have proved to be the most important of all possible multidentate chromogenic ligand
systems,available for metal-complex formation.
M
X X
X X
M
X
X
X
L
L
L
M
X
X
X
X X
X

1:1 metal dye complexes
These are tridentate structures in which the three remaining sites on the chromium (III) ion are occupied by
colorless monodentate ligands.
O H
2 O H
2
O H
2
NaO
3
S
Cr
O
N
N
N
N
O
O
2
N

C.I Acid Orange 74
These are quite stable at low PH values.
1:2 metal dye complexes
The unfilled sites in 1:1 metal dye complexes of chromium (III) or cobalt (III) ion can be occupied by colourless
ligands (three mono-,mono/bi or one tridentate).
X
X
N
N
NH
O
Co
N
N
O
NH
O
O
O
O

C.I Acid yellow 119 (X=NO2)
C.I Acid yellow 151 (X=SO2NH2)
Quadridentate ligand systems
For trivalent metals of coordination sphere is completed using a colourless ligand molecule such as pyridine,
ammonia or water.
X
X
X
X
M
X
X
L
L
X
X
M

Metal complex colorants
Copper complexes
The only copper complexes of tridentate azo compounds are 1:1 structures of tridentate azo compounds are
1:1 structures,since copper (II) has a CN of 4.the major application for copper-complex azo dyes is a direct or
reactive dyes for the dyeing of cellulosic fibres.
They are seldom developed for use on wool or nylon,although various orange and red 1:1 copper complex azo
pyrazolones were synthesized.
O H
2
N
N
N
N
NH
SO
2
H
3
C
O Cu
O



Iron complexes
Iron complexes of tridentate o,o-dihydroxy azo complexes are prepared nder eal acidic conditions at -
ot e(II) and Fe(III) salts can serve as iron source.the Fe(III) complexes that result in both cases do not
have sufficient stability to dye textile substrates,but the dyeing on leather have good fastness properties.
The symmetrical 1:2 iron complexes were synthesized by reacting the metal free ligands with iron (III)
sulphate.
N
N
O
2
S
NH
2
N
N
O
Fe
O
X
SO
2
N H
2
X
O O

Cobalt complexes
Preparation of 1:2 cobalt complexes does not require such high temperature as the corresponding 1:2
chromium complexes.the usual method is the reaction of Co(II) salts in alkaline medium at about 60C which
leads rapidly to the diamagnetic 1:2 Co(III) complexes.Co(III) exhibits a greater tendency to form complexes
with nitrogen-donor ligands than with oxygen donor ligands.
N
N
N
N
O
Cu
O
O O
Cl
NaO
3
S
X

Bidentate nitrogen donor ligands,sc as etlenediamine,iganide and dipridl, are even more sitale
for stailizing 1:1 coalt complexes, and tridentate nitrogen-donor ligands, sc as dietlene-triamine and
terpyridyl are even better.
Chromium complexes
Because of their high stability chromium complexes of tridentate azo dyes are the most important class of
metal complex dyes. Generally,1:1 chromium complexes can be made in acid medium below PH 4,whereas 1:2
chromium complexes are prepared at higher PH in weakly acid to alkaline medium.
The 1:1 chromium complex dyes are only stable in the presence of mineral acids,while 1:2 chromium complex
dyes are only stable in the prensence of mineral acids.while 1:2 chromium complex dyes are unstable at high
acidity and disproportionate into the corresponding 1:1 chromium complex and the metal-free dye.
N N
N
N
N
N
O
Cr
O
O O
CH
3
O
N H
2
O
O
R
H
3
C
O
NH
2
R