in Aqueous Solution

Stnbility of Complexes
500
covalent contril.
metals
class bresults from denc
complexes of transter of electron
of the metal-ligand bonds and from the stable com
tion to via r-bonding.The most
ligand S2 and
from the metal the
to
formed with ligands ike PMe,
lexes of class b metals.are like CO CN which have
vac ant
"d-orbitals or
which have vacant
molecularorbitals of, low energy.
constants do not display
For borderline metals the stability
behaviour uniquely.
either class a or class &
of the central ion. The bonding between
(iv) Electronegativity some extent, due to the donation
a central ion and a ligand is, to ion. Thus, it might be con.
to the central
electronsby the ligand with (i.e. a central
cluded that a central ion higher electronegativity
electro-attracting tendency)
would give the most
ion with a strong
stable complexes.
(6) Properties of the Ligand.
in determining the
With reference to the role of the ligands
the following factors are important
stability of the metal complexes,
For charged ligands, the higher
Size and charge of ligaFd. smaller their size, the more stable
thecharge carried by them and the smaller,
which are form
are complexes formed ; e.g., theF° ions, are
the
ions. This
stable complexes than the Cl ions which larger
values of [Fell F2t and
fact is evident from the stability constant Thus for class
[Felll Clj+ ions which are 10 and 20 respectively. a
metals the order of stability of the halide complexes is F*>Cl>
Br->I, but this order: is reversed for class b metals (Pt", Cu
Ag, Hg etc).
For monodentate neutral ligands, the higher the dipole moment
and smaller the size, the more stable are the complexes formed.
(H Basic character of ligands. The more basic is the ligand,
more easily it can electron pairs to the central ion and hence
more easily it can form complexes of greater stability. The ligands
that bind Ht firmly form stable complexes with metal ions. Thus
F should form stable complexes than Cl, Br or I, and NH,
should be better ligand than H0 which in turn should be better than
HP. This behaviour is observed for alkali, alkeline earth and other
electropositive metals like first-row transition elements, lanthanides
and actinides.
(i Chelate effect. Complexes containing chelate rings are
usually more stable than similar complexes containing no rings, 1.e.
multidentate igands (chelating ligands) in general formn more stable
complexes than the monodentate ligands. This is termed as chelate
effect. This eifect is obvious from the values of stability constants
of Ni-NH, and Ni+-en systems
Ni(ag)+6NH,(ag) [Ni(NH).+(ag), log B-799
Niag)+3en (aq) [Ni(en),*(ag), log B 18'1
 Cability of Complexes in Aqueous Solution
501
Note that
NHg is a monodentate ligand while
NH-CHaCHNH (en) is a ethylene diamine,
amplex [Ni (en)al*T 1S much morebidentate ligand. Obviously the
stable than [Ni(NH,).13+, since
he former complex contains
cheate rings while the latter one has
elate ring. The chelate effect is 3s0 cvident no
Cility of NH3, ethylene diamine, from the fact that the
NH,-CH-CH -NH, (en) and
thvienetetra aminc, NH-CHah-NH(CH)-NH-(CH,)
NH. (trien) complexes of
Cu 1on is in the order
log Cu(NH)JP*<[Cufen),1+<
12:7
197,
[Cu(trien)]+
order to understand this effect we
In 20-5,
well-known thormodynamic relationship : should note the following
-RT In
B=AG=AH-TAS° (AH is negative)
AG°=Standard free energy change, R=Gas
Here
T=Absolute temperature, AH=Enthalpy constant,
AS°=Entropy change. (or heat) change and
Enthalpy change between chelaied and
is small dueto similar non-chelated complex
metal-donor
the thermodynamic data given atom linkages as is evident
from
for
ing to the formation of non-chelated the following two reactions lead.
and chelated
tively. complex respec
() Cd+ +
4CH,NH,[Cd(NH,CH,)J+
Monodentate Non-chelated with log B=652,
ligand
complex1 AWSa
AH-57-3, AS°-67-3,-TAS-201 and
AG°=-37-2
Cd+
(ti) + 2 en
Bidentate (Cd(en)*
Chelated
with log B=10-6,
ligand complex
AH--563, AS°+141,-TAS°-42 and AG°-607.
All the
thermodynamic data are given in KJ/mole.
It follows from the above
becomes more negative. The value relation that ß increases as AG°
of AG becomes more
when that of AS° becomes more positive (see negative
tive value of AS will lead to a more negative above), i.e. more posi-
hence a more stable complex is formed. In the value ofof AG and
dynamics the equilibrium constant of a reaction language thermo.
the is the measure of
heat released in the reaction and the
Teaction. The greater the amount of heat entropy
released
change during the
10ore stable are the reaction products. The entropyinofa areaction, the
neasure of the amount of disorder. The greater the amount system is a
order produced in the products during the reaction of dis
ants, the greater the increase in entropy relative to the reac
ence the'
greater the stability of the producis. during the reaction and

The fact that the

stability, of the complex increases with the
rcase of entropy can be illustrated by
uc ethylene diamine molecple, the folowing example
NHa-CH-CH-NA, (en) is
 Stability of Complexesin Aqueous Solution

502
with hydrated complex
ion, bidentate
0), it replaces
[M(H,0).P+
ligand.
react it is a
allowed to from it, since
molecules
two H,O (M(H,O)t+en [M(H,O,(en)]++2H,0

particles in th.
the number of ystem
increases ntropy.Thus the complex,
This process disorder and
its [M(H,O),P+.
and hence is m o r e
stable than
[M(H,OU(en)**

explanation or
the chelate effect
Following sidgwick the
bondbe
the two metal-ligand
pictorially. If one of bond still re
a
presented more remaining
broken, the broken nDs
bidentate chelate system is the bond can be r
metal ion so that bond of a monod
attached with the
other hand if the metal-iigand
lished. On the
complex (non-chelated
is broken, the ligand will ave
complex) Thus a chelated complex
tate
from the vicinity
of the metal ion.
away complex and hence will repist
a non-chelated
dissociates less than
constant. This explanation is illustrated by the
a higher stability
following example:
non-chelated comp.
T h e removal of an NH, molecule from thebreaking of the bond
results in
lex, [MNH,)P+ in aqueous solutionviz. NH, molecule moves away
and the displaced ligand molecule
the metal ion, M But when one bond of the
from the vicinity of[M(NH-CH-CH-NH),J* is broken, the
chelated complex,
ligand, NH-CH
metal ion, Ma+ still remains attachedhencethe
to
and displaced-NH, is not
CH-NH, by the second bond metal ion.
allowed to-move away from the

2 2
CH HN CH2
-NH2 ONE NH,

M BOND
BROKEN
NH2 NH2 NH2 NH
N
2
CH2 CH

Thus there is greater possibility of the reformation of the

broker bondin the chelated complex than in the non-chelated com
plex. This explains the greater inherent stability of a chelated com
plex as compared to a non-chelated complex.
(v)-Chelate ring size. The largér the number of the chelate
rings in a complex, the greater is its stability. This is illustrated n
Table 148.
Stabilt of Complexes in Aqueous Solutlon
503
Table 148. Overall stability constant values (ie. log1o B
e ammonia and poiyamine
for $o helate ring size on the complexes illustrating the etfet "of
values)
stability of the complexes.
The abbreviations used this
in Table have the following
meaning
en ethylene diamine, NH,CH,CH,NH
trien triethylene tetramine,
tren triamino triethylamine,NH,(CH,),NH(CHa)NH(CH ) NHa
dien- diethylene triamine,
(NH2CH,CH)aN
nententetrakis (aminoett NH4CH,CH,NHCH,CH
yl) ethylene diamine,
NH
M Metal.(NH,CHCHanNCH,CHN(CH,CH,NHah
Values of stability constants
Metal No. of (log1o Bvalues)
complexes chelate rings
Mn+
Fe+ Co+ Na+C+ Z+ Ca+

M(NH)
237 S31779 12:59 9-06 6-92

M(en) 49 7-7
109 14S 202 1112 10:3

M(trien) 78 110 141 205 121 100

M (tren)
128 140 188
146 12:3

M(dien 70 104 141 18-9 213 144 138

M(penten) s
4 112 153 119-3 224 162 162

Table 14-8 clearly shows that

rings in the complex, the greater is the greater the mumber of chelate
the stability of the
complex.
The stability of the complexes also depends on the
theatoms present in the ring. The number of
chelates containing 3-membered
ring inckuding the metal are very unstable and hence are unknown.
4membered chelate rings are rare a: d occur in carbonate (1), nitrate
(nd sulphate (III) chelates.
Mc-0, 0
N=O, S=O
(1).
The most common and the most
stable.chelates are 5- and 6
nembered chelates. 5-membered chelates
Lan the 6-membered chelates when the atoms frequently
are more stable
in the ring are joined
y Single bonds only. On the other hand 6
ofe stable
than 5-membered chelates of membered chelatesorare
heterocyclic ligands of
 Stability of Complexes in
504
Aqueous Solution
ligands involving conjugation in the chelate ring,
acetylacetone complexes of the meta jons which conta which For example,
contain 6-mem.
bered conjugate chelate rings are more stable than
the correS
ponding ethylene diamine complexes wlhich contain only
chelate rings. In acetylacetone complexes the r-electron
spread up over the whole ring which increaseg the
the sta:
5-membere
density gets
6-membered ring system.The possibility of the reso stability of thithis
chelate ion is an additional factor contributi nce in its
acetylacetone complexes.
CH3 CH
O-0
HC M M CH
C=O
o-
H,C CH
() Steric effects. When a bulky group is either attached to
or present near the donor atom of a ligand, mutual repulsion amono
the ligands occurs and consequently the metal-ligand bond
weakened. Thus large bulky ligands form less
do the analogous smaller ligands. This effect stable complexes than
is commonly referred
to as steric bindrance (steric effect
or steric strain). This effect can
be illustratecd by the following examples:
(a) eti ylene diamine, NH-(CH)-NH, complexes are more
stable than those of tetramethyl ethylene diamine, (CH,}N-(CHh
-N(CH,)h which is the tetramethyl substituted derivative of NH
(CH-NH. Thus:
[M(NH-CH-CH-NH,)*
[M(N(CH>)»-CH-CH-N(CH,h*
(b) Complex of Ni2+ with 8-bydroxy quinoline is more stable
than that of 2-methyl-8-hydroxy quinoline. Thus

Nt CH Ni
(ogB-218 (logB17:58)
The strain effect is sometimes due to the geometry of ligand
coupled with the stereo-chemistry øf the metal complex. For example
triethylene tetraamine, NH (CH NH(CH-NH-(CHa
NH, (trien) can coordinate its all the four nitrogens at the corners
a square but triethyltriamine, (NH-CH CHN (tren) can not
so. Thus straight-chain in trien forms more stable.complexes w
Cu+ ion than does the branched-chain in tren becausé rren is una
to assume the preferred square planar geometry.
Stability of Complexes in Aqueous Solution 505
Other Factors
The amount of
olis
the stability of the metal-ligand covalent character also influences
complexes of relatively electronegative metals
those in copper and zinc families and Sn and Pb. For example like the
order of stability of the
complexes, [AgX,] and [AgX3]is as
Agl AgBr>AgCl AgFa
Agl AgBr AgCl AgFa
This order is attributed to the increase in covalent character in
Ag-X bond from Ag-F to Ag-I.