NeU

7) and
Stability of Complexes
Reaction Mechanism

Pbilityof a complex compound is assigned to be its existence in

hond dissociation energy, Gibbs free energy, standard electrode aqueousorsolution with respect to
ts constant or activation energy for substitution reactions. On potential pH of the solution and
account of these parameters stability of
complexes is of two types.
Thermodynamic stability and
Kinetic stability

THERMODYNAMICSTABILITY
Thermodynamic stability of a complex refers to the tendency to exist under equilibrium conditions.
nother words,we can say that the thermodynamic stability of a complex is the measure of tendency of a
metal ion to form a particular complex ion. Thermodynamic stability is directly related to metal-ligand
bond energies. The thermodynamic stability of a complex is given by formation constant (also called the
Sablity constant which is the equilibrium constant for the complex ion formation).
In general complexes are not prepared from their components in gaseous phase but these are
Pepated in aqueous solution. In aqueous solution a metal cation gets hydrated to give, [M(H,0), j"*
plex 1on. When a ligand replaces water molecule from aqua complex ion, a new complex ion is
formed and an equilibrium is established as shown below:
Kf
[M(H;0),j"* +L [M(H,0),-L]* + H,0 ...(i)
Where xis the number of water molecules, nis the oxidation number of the metal cation and Lis the
neutral and the above rreaction can be written in generalized form as
gven below monodentate
: ligand. For simplicity,th
Kf
M+L ML ..(ii)
The equilibrium constant of the reaction is given by :
[ML] ...(iiü)
Kf [MJ[L]
solution ofthe metal complex and it is incorporated
Concentration
Ito K.The water constant in dilute
ofmolecule which enters the bulk solution does not affect the equilibrium constant.
H,0 is
 7.2
Coordination Chernistry
Higher the value of K, more will be the stability of the complex formed. A high
cquilibrium constant (K, >i0) indicates that at equilibrium, acivity of complex ML is lager thvalue Ofof
product of activities of Mand L. Thus, large value ofK, indicates that ligand L binds to the metal
more strongly than H,0 andhence Lis astronger ligand than H,0. IfK, is less than 1.0, then ligandOion
weakerThethan H;0. Thus, stability constant is used as ameasure ofthermodynamic stability of compler
formation constant (K) is related to the standard Gibbs free energy change and standard
electrode potential according to following relation :
AG°=-RT In K, .iv)
and AG°= -nFE°
...(v)
and RT In K = nFE° ..(vi)
Since AG° is a thermodynamic property thus formation constant is the measure of thermodynamie
stability.
The cquations (iv), (v) and (vi) indicate that the thermodynamic stability of a complex can be
measured in terms of formation constant, AG° and standard electrode potential. Ahigh negative value of
AG° (or a high positive value of E") indicates that the position of equilibrium favours the produet
(complex) i.e, high negative value of AG° indicates that the complex formed willbe more stable.

Stepwise Formation of Complex and Stepwise FormationConstants

The extent to which a metalcation combines with ligands to form a complex ion is expressed in
terms of formation constant. A complex is formed by substitution of water molecules by other strong
ligands from aquated metal ion in an aqueous solution. When more than one water molecule of hydrated
metal cation, [M(H,0),j* are replaced by another neutral and monodentate ligand L, then it is
assumed that this may occur in several steps and each step is characterized by its individual equilibrium
constant called as stepwise formation constants (or stepwise stability constants). For a general case of the
formation of complex ML, from an aquated metal cation [M(H,0),, 1* and monodentate ligand L,
there will be n consecutive steps and n stepwise formation constants.
KË [ML]
M+LML K1
[MJ[L]
K2 [ML2]
ML LML
+ K2
[ML][L]
K3 [ML3]
ML, + LML3 K3 ...(1)
[ML2][L]
Kn [ML,J
ML-l +L ML, [ML-lLI
Bn [ML,J
M+nL ML, B, =
[MJ[LI"
constants or stepwise stability constants
Where Kj, K2, K3, ....., Kn are the stepwise formation
where Bn is overall formation constant or overall stability constant.
follows
Ihe formation of complexes ML, ML2, ML3.......ML. may also be expressed by the
steps and equilibrium constants B1.B2.B3,....B, respectively.
 Stabilityof Complexes and Reaction Mechanism 7.3

M+L ML [MLJ
Bi
[MI[L]
B2
M+2LML2 B2 = [ML2]
[MI[L1
B3
M+3LML3 B3 = [ML;]
(M|[LJ'
Bn
M+ nLML, B, = [ML) ...(2)
[M][L]"
Where B1.B2.B3,.B, are the equilibrium constants called as overall (or cumulative) formation
constants.
constants or overall stability

Relationship between K1,K2,.. K, and Bn

Consider the expression for B3
[ML3]
B3 = ...(3)
[MI[LJ*
Onmultiplying both numerator and denominator by [ML][ML2]and then rearrange
B3 = [ML3] [ML2][ML]
[MJ[L]' [ML; J[ML]
[ML] [ML;] [ML;]
B3 =
[MJ[L]'[MLÊ[L]'(ML2 J[L]
B3 = K1.K2.K3 ... (4)
Therefore, Bn = KË. K, .K3......... K, ...(5)
and
log B, = log KË + log K, + log K3 +.....+ log K,
bquation (5) indicates that the overall formation constant (B) is equal to the productof the stepwise
lomation constants Ki.KT. Ka.......K,. Also equation (5) indicates that the formation of a complex
takes place in various stepwise
equilibria.
e ofnverse
constant of the formation constant (Kr)is called the dissociation constant (K) or instability
the complex.
Kd
MLn M+nL

KA =
[MJ[L]"
[ML,]
The
formation dissociation constant gives a measure of the extent to which the equilibrium representing the
of a complex lies to the right.
 7.4 Coordination Chemistry
Trends in Stepwise (or Successive) Formation Constants
With afew exception, it is commonly observed that the magnitude of stepwise formation
decreases steadily from KË to Ky
K > K2 > K3 >....> Kn-1 > Kn
NH; complex and (ii) Cd+ -CN complexes.
This trend is illustrated by : (i) Cd
ca2t + NHCd(NH3 ))* KË = 102.65
()
Ky = 102.10
[Cd(NH3 )j* + NH;Cd(NH3 )21+
[Cd(NH3):]* + NH Cd (NH3 )31* K3 = 10l.44
K4 = 100.93
[Cd (NH; )31* + NH3[Cd (NH3 )4 ]*t
B4 = KËK, K3 -K4 = 10265 . 102.10 .1044 .100.
-100.93
=107.12
K, = 10548
(ii) ca? +CN Cd(CN)J
[Cd(CN)J +CN Cd(CN)2] Ky = 105.12
Cd(CN)3] K3 = 104.65
[Cd(CN)2 ]+ CN
[Cd(CN)3] +CN Cd(CN)4 1 K4 = 103.55
B4 =10548 .105.12 .104.65 .103.55
=1018.8
The steady decrease in the value of stepwise formation constants from KË to K, is due to :
i) increase in number ofligands in coordination sphere causes to decrease the number of H,O molecules
to be replaced and thus the probability of replacement of water molecules decreases. (i) electrostatic
factors (when charged ligands are involved) (ii) steric hindrance increases with increase in number of
ligands (iv) statistical factors.
However, in some cases it is found that K+ 1 > K, because of unusual structure change and
change in electronic structure (ie., change in spin state) of the metal ion.
Change in electronic configuration causes the change in CFSE and the complex with more value ot
CFSE will be more stable and the equilibrium constant for that complex formation will be high.
Consider, for example, the formation of [CdBr41 complex ion in aqueous solution. The formato
of [CdBr4 1 complex with Br exhibit four stepwise equilibrium or stepwise formation constanis
K, K2, K3 and K4. The order of stepwise fornation constants is observed as follows
KË > K; > K3 < K4 which is contrary to KË > K2 > K, > K4.
Aqua complex of most of the M²* ions are octahedral whereas the halo complexes of Ca
generally tetrahedral. The reactions for the formation of[CdBr4 1 are :
KË
(Cd(H,0)%]* +Br [Cd(Hz0)s Br]" + Hz0
K2
[Cd (H,0), Br]" + Br [Cd(H,0)4 Br2]+ H,o
 Stabilityof.Complexes and Reaction Mechanism
7.5

K3
[Cd(H;0)4 Brz ]+ Br Cd (H,0); Br3 ] +H0
K4
[Cd(H;0)3 Br3 ]+ Br [CdBr4 ] +3H,0
mlast step is favoured by the relcase of three HOmolecules and simultaneously there is unusual
structuraland clectronic configuration change and thus K4 > K3 .
Furtherconsiderranother example of formation of[Fe(bpy)3 ]2+ from aqueous solution of Fe 2+ ion.
The formation of [Fe(bpy)31* complex ion with bipyridyl takes place in three steps and order of
stepwise formation constants is K1 > K2 < K3 which is contrary to Kj > K) > K3. The reactions for
are :
the formation of[Fe(bpy)3 1*
KË
[Fe(H,0)6* +bpy [Fe(H,0)4 (bpy)] +2H;0
K2
[Fe(H;0)4(bpy)]* +bpy [Fe(H;0)2 (bpy)2 ] +2H,0
K3
[Fe(H20)2 (bpy) 2]+ bpy [Fe(bpy)3]*+2H,o

The two complexes [Fe(H,0)4 (bpy)]* and [Fe(H;0)2 (bpy) >I* are high spin due to the
presence of weak H0ligands having t 4 eo electronic configuration with CFSE of- 0.4 Ag.
The complex [Fe(bpy) 3j+ formed in last step is low spin 6
due to the presence of only strong
bipyridyl ligands. This complex have electronic configuration g eg with CFSE of-2.4 A,. Therefore,
there is change in electronic configuration and increase in CFSE. Hence, K3 >K2.
FACTORS AFFECTING STABILITY OF COMPLEXES

The factors which determine the stability of complexes are :

(1) Nature of the Central Metal Ion (2) Nature of the Ligands
(3) The Chelate Effect (4) Macrocyclic Effect
(5) Resonance Effect (6) Steric Effect or Steric Hindrance

(1) Nature of the Central Metal lon

metals ions
Variations in the stabilities (i.e., stability constants) for a series of complexes of
with a common set of ligands.
(a) Charge on Metal Cation : In general, a metal cation in higher oxidation state form more stable
Complexes than that of in lower oxidation states with a given ligand like X or NH3 or H,0.CN However
there are a few exceptions with ligands such as CO, PMe3, 0-phenanthroline, bipyridyl, which

form more stable complexes with metals in lower ofoxidation states. These ligands have vacant t
metal atom or cation and
molecular orbitals bonding.
for accommodation of lone pair electrons donated by
hence for T-back The electron rich CN is not only a poor T-acceptor but is also a good
G-donor and, therefore, forms complexes with metal atoms in higher oxidation state.
7.6
Coordination Chemistry
(b) Size of Central Metal Cation : For agiven ligand and metals of same oxidation
of the complexes increases with decrease in size of metal cations. For M2+ ions, the states, stability
stability for complexes is general trend in
2+
Ba2* <Sr2+ <Ca?t <Mg?* <Mn2 <Fe?* <Co?t <Ni'* <Cy2+,> Zn2+ z24
This trend in stability is known as Irving-Williams series.
This order of stability is consistent with charge to radius ratio concept because the radii
from Ba toCu 2+ and then increases to Zn. The order of size of depositive ions is : decrease
Ba2t >Sr2t > Cat> Mg*> Mn+ > Fe2+ > Co2+ > Ni>Cu<Zh2+
Since size of Zn is larger than that ofCu ion, therefore, stability of Zn complex is lower than
that of Cu2+ ion.
Aplot of log Kof complexes of M* ions with oxalate ions is shown in Figure 7.1. The lop K.
values of Ba,Sr*,Ca,Mg, Mn (HS complex) and Zn complexes lies on aline because their
is no additional CFSE (i.e., CFSE = 0).
Though CuIl) complexes have an additional e antibonding electron, they are more stable than
Ni(I) complexes. This is due to the Jahn-Teller distortion. During the distortion two electrons are
lowered in energy (d,) while only one electron d2_,2 orbital is raised by an equal amount in energy as
compared to octahedral field. It results in strong bonding of four ligands in the xy-plane of tetragonally
distorted Cu(l) complex and increases the value of formation constant. The axialpositions are weakly
bound which is responsible for higher lability of complex.

10

NH,CH,CH,S
log
K,

OX

2
gly

den

Ba Sr Ca Mg Mn Fe Co Ni Cu Zn

Figure 7.1 Variation of formation constants for M² ions of Irving-Williams series.

 Stabilityof Complexes and Reaction Mechanism 7.7

The value of stability constant for octahedral complexes of Mn to Cu ions increases more
rapidly because these ions are additionally stabilized by CFSEs in octahedral field (Figure 7.1). The
stabilityoffoctahedral complexes of Zn* is lower than that ofCu jon because its CFSE is zero and it
the line representing the stabilities of BaS2+ .Ca,Mg and Mn 2 jons where CFSE is
lies on
alsozero.
2as a' andClass b° Metals : Ahrland-etal in 1958 have classified the metals intothree
basis of their electron acceptor properties :
categories on the
(i)Class 'a' metal
metals
(ii)Class b'
(i) Borderline metals
Csg' metals : Class a metal ions are characterized by high electropositive character (i.e, low
electronegativites), small size, high oxidation states (+3 or higher) and no easily distorted outer
electrons. These metal ions form their most stable complexes with ligands favouring electrostatic
bonding. Class a metals form their most stable complexes with the first elements of group 15, 16 and 17
(eg., N,O and F)
Class a metal ions include smaller ions from alkali metals, alkaline earth metals, lighter transition
metals in high oxidation states (+3or higher). Class a metals are also called as hard acids or hard metals.
Mg.Ca2Sr2+ AJ3+ ,Ga3+,Ih34
Class ametals (or hard metals) are H, Li", Na, K, Be,
,La3+,Ce3+,Gd3+ 4+ Hr4+ Th4+ Pu 4+ etc.
Se3+ ,In 4+ Cr3t , Mn ,Fe +,Co3+
following donor
The order of stabilities of complexes of class 'a' metals with the ligands having the
atoms is as follows :

F>CI> Br>
O>>S> Se >Te
N>>P> As > Sb
'5 metals : Class 'b' metals are less electropositive, have relatively full d-orbitals and
(1) Class
most stable complexes with ligands which, in addition to possess lone pairs of electrons, have
Om their electron pair from the d-orbitals of the metal. Class
b
t-orbitals available to accommodate
piy
stable complexes with ligands which have donor atoms from period 3 or subsequent periods.
Om
bond in these complexes is covalent. The order of stability is the reverse of class 'a
e metal ligand in heavier elements favours an increase
in
in availability of empty d-orbitals
Ctak'ne increase called as soft acids or soft metals.
aoy of the complexes. Class b metals are also having the following donor atoms is as follows:
ligands
e order of stabilities of complexes with
F <CI < Br <I

O<<S < Se < Te

N<<P<As < Sb
complexes with CO, o-phenanthroline, olefins because
class b' metals form stable
theseFurthermore,
have vacant TI-orbitals of low lying energy.
7.8
Coordination Chemistry
Class 5' metals are :
P:4+.T73+, etc.
1,Ag,Au,TI,Cd,Hg, Hg +,Pd+ ,P2+,
(ii) Borderline Metals : Borderline metals include dipositive metal ions of 3d-serjies whit
Mp2*, Fe2t.co2t, Ni2*,cu2*,zn2*.For agiven ligand order2+of stability of complexes is :
Mn 2t < Fe2t <Co2+ <N/2+ <Cu 2+ > Zn (Irving-Williams series)
According to Pearson hard metals or acids prefer to bind to hard bases or hard ligand and end..
or metals prefer to bind to soft bases or ligand.

(2) Nature of Ligands

()Basie Character of Ligands : In general, more is the basic character of ligands, more easily it
can donate its lone pair of electrons to the central metal ion and hence greater is the stability of the
complex formed. For example, for a given dipositive (M*)3d-series transition metal ion, order of
stability of complex with NH3, H,0 and F is:
NH3 > H,0> F
(i) Covalent Characeter :Higher the covalent character, higher will be the stability of the complex.
For example,order of stability and covalent character of complexes of Ag" with halogen is:
Aglz > Ag Brz > Ag Cl, > AgFz
Decreasing order of covalent character’
Decreasing order of stability of complex’
(ii) n -Bonding Capacity of Ligands : The ligands like CO, CN,alkenes, phenanthroline,
bipyridyl, RzP, R2S, etc have vacant - or d-orbital to form - bond and hence form stable complexes
with metals.
(iv) Dipole Moment of Ligands : For neutral ligands, higher the magnitude of dipole moment,
higher will be the stability of the complex. For example, the order of stability of complexes of ligands
having N as donor atom is :
ammonia> ethylamine > dicthylamine> triethylamine
(3)The Chelate Effect
The polydentate ligands (with more than one donor atoms) have geometries such that they can o
more than one coordinate bond to the same metal cation, such ligands are called chelating ligands. 1e
ligands, generally are non-linear. The complex formed by the coordination ofa polydentate ligand
metal cation is called a chelate complex or a chelate.
(containing
Chelating ligands form more stable complexes than the analogous monodentate ligandsnon-chelated
the samne donor atom). It means that chelated
complexes are more stable than their
analogs.This effect is called as chelate effect.
Let us consider the formation of complexes from hydrated cadmium ion, [Cd(Hz0)4 ere
methylamine (CH3 NH2), ethylenediamine (en) and triethylenetetraamine (trien) ligands. Where
methylamnine (CH3 NH2), ethylenediamine (H,N -CH, CH2 - NH2) and triethylenetetraamine
 Complexes and Reaction Mechanism
Stabilityof 7.9

,N--CH2 CH2- NH. CH)-CH2 NH-CH)-CH2- NH2) are monodentate,

(H,N andtetradentate ligands respectively.
bidentate
[Cd(Hz0)41+ +4CH;NH2 [Cd(CH; NH2 )4]+ +4H,0 ...(i)
[Cd(H;0)4]* +2 en [Cd(en) 21* +4H;0 (5) choye un no. o...()
(3) Imolecules
[Cd(H;0)41* + trien [Cd(trien) +4H,0 ..(ii)
Cuactures of [Cd(CH3 NH2 )4 [Cd(en)2] and [Cd(trien)] are shown in Figure 7 2
12+
CH;H,N NH,CH3 * |CH2 H,N NH2 CH2
Cd Cd
|CH3H,N NH,CH, |CH; H,N NH2 CH)
(a) (b)
12+

CH2 H,N NH, CH,

Cd
CH2 NH NHCH)
CH, CH,
(c)

[Cd (en >]+, (c) [Cd (trien)].

Figure 7.2 Structures of : (a) [Cd(CH,NH, 4J (b)
non-chelated complex ion whereas [Cd(en)2]* and [Cd (trien)] are
[Cd (CHzNH, )4]* is a
(CH; NHT )41 is less stable than [Cd (en)2]* and [Cd (trien)]". It
cnelated complex ions. Thus, [Cd
ion. Therefore, order of
observed that [Cd (trien)] is more stable than [Cd (en)» 1* chelate
diso
Stability of these complex ions is : (trien)]*
]* <[Cd
(Cd(CH3NH, )4 1* <[Cdbe(en)2
explained in two ways :
can
Ihe above order of stability of complexes (CH3 NH, )41* is formed and there is no net
1. In reaction : (i) a non-chelated complex ion [Cd the
and (ii)
other hand, in reaction(i) Since
of reaction. On reaction.
change in the number of molecules and entropy hence there is an increase in entropy of Therefore, the
there is an increase in number of molecules and (ii)
(iii) is greater than that of reaction the above three
Increase in number of molecules in reaction reaction (ii). Since bonding in all
(iii)
reaction than and negative in sign.
increase inis entropy(i.e.,
1s greater in
Cd Nbond) thus, AH° in allthe three reactions is same
in terms of AG°. FFor
a stable complex
reactions same, of a complex is expressed
stability
AG° isThermodynamically,
the
negative and large. AG°= AH°-TASO
increases from reaction (i) to (ii)) to
same and entropy from reaction(i) to
reactions is and increases
Since AH° in all the above three be negative in the three reactions
(im) and thus, free energychange will
() to (ii).
 7.10
Coordination Chemistry
A large negative value of AG° indicates the large value of stability constant (K)
because AG°= -RT In K
Thus,order of stability of the three complexes is :
[Cd(CH; NH,)4 ]* <[Cd(en)2 1* <[Cd(trien)]*
2. CH,NH,, en and trien ligands are competing for the formation of complexes with Cq2+ ion in
aqueous solution, the probability of either of them coordinating to the first site may be taken as
equal.
Once one end of en or trien is attached to Cd ion, it is seen that the second amine group of en and trien
is now greater in vicinity ofCd ion than the secondCH3 NH, ligand which is free to move rand
the solution. Thus, probability of secondamine group of en or trien to attach to Cd jon isgreata
that of monodentate ligand CH; NH2. This indicates that formation constant is larger for the formati
chelates.
Further, the third and fourth donor atoms (amine groups) of trien are now greater in vicinity whereas
the second en and the monodentate ligand CH; NH2 are moved freely and randomly in the solution,.
Thus, probability of third and fourth amine groups of trien to attach to Ca" ion is greater than that of en
and CH,NH, ligands. This indicates that stability of complex increases with the denticity of the ligand
(denticity of a ligand is the number of donor atoms). In other words, we can say that the chelates in which
one ligand form two or more rings are more stable than the complex in which one ligand form only one
ring or no ring. The dependence of stability of chelates on the size of chelate ring is shown in Figure 7.3.

COO
7+
COO
6 COO

5 CH,
log
K
COO
4t

3
CH,-C00
2
CH,-COO
1

Mn2+ Fe2+ Co2+ Ni2+ Cu2t Zn2t

Figure 7.3 Dependence of complex stability on the size of the chelate ring.
Imore stablethan siX
In general, the chelates having five membered rings (including the metal) areThus, the chelate effect
membered rings which are in turn more stable than the seven membered rings. and 6-
pronouncedfor 5- the
weakens as the ring size increases. The chelate effect is usually most stable. When
membered rings. Smaller rings generally involve excessive strain and become less
Stabilityof Complexes and Reaction Mechanism 7.11

chainsand
rings become much larger,the enhancement of local concentration (i.e., vicinity of second
atomoff bidentate ligand) decreases and the resulting complex becomes less stable.
donor
Furthermore,forthechelates formed by different bidentateligands of samesize withthe same metal,
order, for example, oxalate <glycinate<ethylenediamine.
stability will| be in the
the
(4)MacrocyclicEffect
Macrocyclic ligands are large ring size compounds even without a metal atom present and these
several donor atoms inside their rings to form coordinate bonds with a metal ion.
ligands have
Chlorophyll, heme and vitamin B2 all contain tetradentate macrocyclicligands. As stated earlier the
more stable complexes than analogous monodentate ligands and the macrocyclic
chelating ligands form size
lgands ofappropriate form more stable complexesthan chelating ligands. There is a competition
ligand and a macrocyclic ligand (a cyclic multi dentate ligand) having the same
between a non-cyclicand
type of donor
atoms the complex formed by macrocyclic ligand will be more stable. This effect is
contain tetradentate (four N-donor
lled as macrocyclic effect. Chlorophyll, heme and vitamin B12 all
atoms) macrocyclic ligands.
(5) Resonance Effect
anion ligand shows
Resonance enhances the stability of complexes. For example, acetylacetonate
resonance and form stable chelated complex.

CH; -C-CH =C-CH3 ’ CH3 - C=CH-C-CH;

and strength.
As a result of resonance the M0bonds are equal in length
(6) Steric Effect or Steric Hindrance
group is either attached to donor atom or to the atom adjacent to donor atom, the
Ii abulky decreases. This effect iscalled steric
complex
metal-ligand bond becomes weak and the stability of the
effect. For examples :
diamine (H,NCH, -CH, - NH, ) and N- tetramethyl ethylenediamine
) Ethylene ligands and form chelates with Ni ion as shown
(CH3)2 N-CH, CH, N(CH),both are bidentate
in Figure 7.4.
H,C 12+
12+

H5C CH3
NH2 CH,-N
N
CH,-H,N NH2
CHs
\cHs
H;H,C
NNCH
|CHH,N NH, CH,
NH2 CH, H,C
H,C CH,
CH
(I)
() Figure 7.4
complex ( ) the methyl groups attached to donor
The complex (II) is less stable than (T) becausein of complex.
atoms create steric hindrance and decreasethe stability
7.12

quinoline both
Coordination Chemi
are bidentate
stry
(i) 8 hydroxy quinoline and 2-methyl-8 hydroxy ligands and form
chelated complexes with Ni ion as shown in Figure 7.5.

N NCH

2 2

() (I)
Figure 7.5

The complex (1I) is less stable than complex (I) because in complex (II) abulky group is atachei
an atom adjacent to donor atom which causes asteric hindrance and lowers the stability of thecomnlew
The chelates containing chelating ligands with delocalized electronic structures are also stabiid
by electronic effect in addition to entropy effect. The examples of such type of ligands are diine
ligands such as bipyridine and o-phenanthroline. These ligands stabilize the complexes because ofther
ability to act as G-donors as well as t-acceptors. These ligands form r-bonds by overlapping their emmy
ring *orbitals with filled metal d-orbitals. An important example of such type of complexesis
[Rubpy) : ]* (Figure 7.6).
2+

Ru

Figure 7.6

KINETIC STABILITY: LABILITY AND INERTNESS

Kinetic stability refers to the rate of reaction which is governed by its activation energy, Ea
constant. Kinetic stability relates to how fast a compound reacts rather than to how stable it 1s.Ou e
basis of rate of reaction, the term kinetic stability is classified into lability and inertness.
The complexes in which substitution of one or more ligands by another occurs readily a f
labile complexes. The ability of a complex to give substitution reactions fastly is called the lability of
that complex. Half-life ('y2) of labile complexes for substitution reactions is less than one minute. The
complexes for whichsubstitution reactions occur slowly (or not at all) are called inert compleexes. Half
life of inert complexes towards substitution
reactions is greater than one
The inability or less ability ofa complex to give substitution reactionsminute.
with other ligands
inertness of the complex.
STABILITY
THERMODYNAMIC
The
STABILITY VERSUS KINETIC under
thermodynamic terms (stable and unstable) refers to the tendency of a complex toexist
equilibrium conditions and the thermodynamic stability is related to the change in free energy, enthalpy
Stabilityof Complexes
and Reaction Mechanism
7.13
entropyofrreaction. The compound may be unstable with respect to a
and
as
Such
light, acid or base.
heat, particular
condition or reagent
Thekinetic,stability (lability: and inertness) refers to the rate of reaction and
as
substitution and electron transfer reactions. mechanisms of reactions
such
the difference between
To illustrate thermodynamic and kinetic stability, considerthe complexes :
n.2.[Mn(CN)6 different.
and
The |CrCN)6.All
rate of
these complexes are thermodynamically stable but
kineticstability is exchange can be measure when
areplaced|in solution with the complex. It is observed that [Ni(CN)41 carbon-14 1abeled cyanideisions
is labile, [Mn(CN)6j less
inert.
labileand[Cr(CN)6] is
[Ni(CN)41 +4CN very
fast [Ni(CN)4 j +4CN
Iy2 =30sec
slow
[Mn(CN)6j +6CN [Mn*CN)6 +6CN
l/2 =1hr
[Cr(CN)6 +6CN-slowest [Cr(CN)6j +6CN
LV2 =24 days

substitution but it is
In contrast, for example [Co(NH3)6* complex ion is inert to
thermodynamically unstable in acid solution.
[Co(NH3 )6j* +6H;0* ’[Co(H,0)6j*+ +6NH,
constant for this reaction is very large (~ 10). This indicates that the complex
The formation
in acidic solution. On the other hand, it takes several days at room
(CONH3 )%" is unstable complex
hence the
nperature to form (Co(HO)6 complex i.e.,the rate ofthis reaction is slow and
(Co(NH3 )6j is kinetically inert. (stable and unstable) are not related to
terms
The above discussion indicates that thermodynamic
kinetic terms (lability and inertners).
OCTAHEDRAL COMPLEXES
REACTION IN
SUBSTITUTIONI of
by another
one ligand in coordination sphere octahedral
the replacement example,
Substitution reactions involvenumber oxidation state of metal cation. Forone labile ligand (say
and (say L) and
without:any change In coordinationor atom boundtofiveinert ligands reaction is shown below:
Ccompl ex containinga metal cation
ligand(Y). The
overall
X) which is to be replaced by an incoming
[MLsX]+Y’ML;Y + X
called nucleophilic substitution
therefore,these reactions are
nucleophile,
Since ligands behave as
Teactions or ligand substitution reactions.
 7.14 Coordination Chemistry
Octahedral Complexes
Mechanism of Substitution Reactions in
of a reaction is the sequence of elementary reactions involved in a
The mechanism
Substitution reactions in octahedral complexes take place through either of the following three reaction,
mechanisms
1. Dissociative (D) Mechanism
2. Associative (A)Mechanism
3. Interchange (I) Mechanism

1, Dissociative (D) Mechanism : In the dissociative mechanism, there is a step in wh:t

intermediate of reduced coordination number is formed i.e., the M-X bond is fully broken before the
M-Y bond begins to form.
+Y
[LsMX] slow
-X
[LsM) fast ’ [LsMY]
Intermediate
C.N. =5

L L
L| L L
M OR M-L
L L L
Square pyramidal L
Trigonal bipyramidal

where L is an inert ligand, X is labile (leaving ligand) and Y is the entering ligand.
The rate determining step is the slowest elementary reaction. The rate of overall substitution reaction
depends only on the concentration of the original complex, [ML;X] and is independent of the
concentration of the incoming ligand Y.
Rate = k [MLsX]
This reaction is of first order in [MLsX]and [ML sX] gets dissociated is rate determining step. Thus,
this reaction is also called dissociative SN' mechanism (substitution, nucleophilic first order).
Most substitution reactions in octahedral complexes takes place by dissociative mechanism in
which an intermediate of coordination number =5(most probable square pyramia) 1S lOu
2. Associative (A) Mechanism : An associative mechanism involyes a step in which an
intermediate is formed with ahigher coordination number than the original complex i.e, the incomin
lhgand Ydirectlyattacks the original complex to form an intermediate with acoordination number =/
the rate determining step. The rate determining step is slow.
[LsMX]+Y slow LM X [L;MY]
k

Intermediate
C.N, =7
 of
Complexes and Reaction Mechanism 7.15
Stability

X Y
L L -M
M OR
L L
L Y L
Monocappcd
octahedron Pentagonal bipyramid
intermediate might be expected a monocapped octahedral structure in which the Xand Y
This second step is the
share one of the octahedral sites or a pentagonal bipramidal structure. The
ligands
dissociation of ligand Xto givethe product. The
rate of reaction depends on the concentration of both
MLXandY.Therefore,
Rate = k[ML^X|[Y]
mechanism is also called SN (Substitution.
This reaction is of second order and this associative
mechanism.
nucleophilic, second order)
place in one step without forming a fairly
3. Interchange (T) Mechanism : This mechanism takes exchange in a single step forming an
stable intermediate, instead the leaving and entering ligandsmany reactions of octahedral complexes.
for
activated complex. The interchange mechanism is common has very little or no stabilization energy and
complex (also called as transition state)
The activated
the reactants.
immediately passes on toproducts or reverts to

LsMX +Y’ [Y.....L. M...X]-’ [Ls MY]+ X

Activated complex
move away from the metal and the
to break and starts to
In this mechanism the M-X bond begins moves into the coordination sphere and no stable
simultaneously and Y
M-Y bonds begins to form
intermediate is formed.
Interchange mechanism is subdevided into two categories
() Interchange Dissociative (Id)
(ü) Interchange Associative Ia) ): The M-Y bond begins to form
before the M-X
) Interchange Dissociative Mechanism closer to a
breaks preferentially and the interchange is
bond is fully broken but the M-X bond
asoClative than to an associative mechanism, and no detectable intermediate appears. before the M-Y
Associative Mechanism ( ) : The M-X bond begins to break
"nterchange
preferentially and the interchange is closer to associative
bond is fully formed but the M-Y bond forms
and no detectable intermediate appears.
DISSOCIATIVE, ASSOCIATIVE
REACTION PROFILES FOR
ANDINTERCHANGE MECHANISMS
called reaction profile or energy profile.
Aplot of pathway is ligand and
free energy versus reaction energy and combines with the incoming difference
In an mechanism a reactant absorbs
formation of product. The
energy
form interchange
an activated complex or transition state before the
energy of activation, Eg. The transition state lies on
betwe n the
reactants and transition state is called
7.16
Coordination Chemistry
the reaction profile (like on top of the hill) and at this point reactant converts into
the top of
without no hesitation [Figure 7.7(a) and
(b)].
deternining step is slow and iif the energy off
product
Ifthe activation energy is high, then the rate
is low, rate determining step is fast.
dissosiative (D) or associative (A) mechanism an
intermediate of lower
activation
In coordination number
(- 5) or higher coordination number (= 7) is formed before the formation of product. Because an
therefore, it will lie in a valley (or bit) iin
is more stable than atransition state,
[Figure 7.7(c) and (d)]. The stability or existing time of an intermediate in a valley dependsenergy
intermediate on howprofile
high
intermediate are :
the energy walls around the
Y-ML--X Y---MLs--X

AG AG
[ML5X]+Y [MLX]+Y
[ML;Y]+X [ML,Y+X
Reaction coordinates Reaction coordinates
(a) (b)
[MLg] +X + Y [(ML]+X+Y

AG AG
[MLGX+Y [MLGX]+Y
[ML,Y+X (ML,Y]+X
Reaction coordinates Reaction coordinates
(c) (d)
Figure 7.7 Energy Profile for : (a) Interchange dissociative (La ), (b)
(c) dissociative (D), (d) Associative (A).
Interchange associative (!2)

INTERPRETATION OF LABILITY AND INERTNESS OF

TRANSITION METAL COMPLEXES
1.On the Basis of Valence Bond
0ctahedral complexes : (i) outer orbitalTheory: According to VBT, transition metals form,two typesof
complexes and (ii) inner orbital complexes. In outer o
complexes, the outer nd-orbitals are involved in
inner (n-1) d- orbitals are spd-hybridization and in inner orbital complexes a
involved in
d'sp'-hybridization.
complexes is larger, weaker and higher in energy whereas in Thus, the M-L bonds in outer
shorter, stronger and lower in energy. inner orbital complexes the
orbital

substitution reactions through

Thus, the transition metal octahedral complexesMing undergoing
would be inert if M-L bond is dissociative mechanism would be labile if the M-L bond is weakmetal and
comparatively
complexes undergoing substitution reactions
strong. Thus, according to VBT, if the transition orbital
complexes are labile and all through dissociative
inner orbital complexes are mechanism then all outer
inert.
 of Complexes and
Stability Reaction Mechanism
7.17
observed that the
Furtheritis
unbybridized complexes either inner orbital or outer orbital are if
metal
lying d-orbitals labile they have
attack for an incoming ligand. Such (below hybrid orbitals). These vacant
low
vacant,
pointof in which an intermediate of complexes undergo orbitals act as a
higher substitution through associative
theinertcomplexes have electron density in thecoordination
mechanism
unhybridizednumber (=7)-1)isd-orbitals.
metal (n formed. OnSome
the example
other hand.of
complexes are shown in Table 7.1:
labileand|inert
Table 7.1
Kinetic No. of Unpaired
Compound Stability Electrons Hybridization
Labile 2
(VNH;)61**
d'sp' -hybridization

Inert 3 1112EEE
d'sp'-hybridization

Labile 4
[MaCl,j sp'-hybridization

0
(CoCN)%j Inert
tsp'-hybridization

can be explained on the basis of CFT. For example,

which
uouga, there are some exceptions complexes have no low d-orbital and,
lying vacantcomplexes
octahedral
ng to VBT d°(HS) .d(HS) and d But experimentally it is observedthat these
are
therefore,these complexes should be inert. reactions
labile. Octahedral complexes undergo substitution place
2. On the Basis of Crystal Field Theory :
(SN) mechanisms. The SN' reactions take
either dissociative (SN') or associative trigonal bipyramidal
through
through the lower energy square pyramidal intermediate
instead of higher
through
energy
pentagonal bipyramidal
SN reactions occurs square pyramidal(C.N,
=
iinntteerrmedi ates. On the other hand, the CFSE on going from
octahedral to negative
CFSE(represented by
mediate(CN =7). There is a changein
(C.N. =
there is loss in complex.
7) intermediate. IfCFSE, more will beinertness ofthe The change
If

sign),pentagonal
then the
bipyramidal
complex will be inert. Higher
the loss in
positive), the complex will be labile. CFSE of the
is zero or
tinhere is no loss in CFSE (i.e., changein CFSEenergy But it is difficultto assignthe calculated
(CFAE). have
CFSE is called as Crystal field activation Basolo and Pearson
knowledge of its
structure. pentagonal bipyramidal
Intervalmediuesate
he or complex without
of CFSE for low
exact
spin and high spin square
table 7.2.
pyramidal and

Intermediates. These values are giventhe

7.18
Coordination Chemistry
Table 7.2 Change in CFSE* on going from Octahedral Complex to Intermediate of C.N. 5
and 7
High Spin Low Spin
C.N. =5 C.N. =7 C.N,=5 C.N.=7
0
+0.57 + 1.28 +0.57 + 1.28
+1.14 + 2.56 + 1.14 +2.56
- 2.00 - 4.26 2.00 4.26
+3.14 - 1.07 - 1.43
-2.98
-0.86 - 1.70
+0.57 +1.28 - 4.00 -8.52
+ 1.14 + 2.56 + 1.14 - 5.34
- 2.00 -4.26 -2.00 - 4.26
+3.14 -1.07 +3.14 - L.07
alo 0

*CESE in unit of D, or A/10 A* sign indicates againin CESE during the process and a- sign indicates
a loss in CFSE.

Since the substitution reactions in most of the octahedral complexes proceed through square
9yramidal intermediate (C.N.= 5) i.e., dissociative mechanism, comparision of inertners or lability is
made on the basis of change in CFSE from octahedral complex to square pyramidal intermediate.
The order of lability of complexes of tripositive metal cations of 3d-series is:
Co (||I) < Cr (II) < Mn (II) <Fe (III) <Ti(III) <V(I)
E.C. d'
Loss in CFSE -4.00 -2.00 -1.43 0.86 +0.57 + 1.14
for SN' mechanism
For isoelectronic metal cations, the lability of complex decreases with inerease in charge on mei
cation because high charge strengthen the M-L bond and reduces the lability. For example, Cr
complexes are more inert than V(a') complexes. Similarly Fed) complexes are more inet
analogous complexes of Mn(a).
It is observed that inertness of analogous complexes of isoelectronic metal cation increases 0n
3d-series
descending within the group because : (i) 4d- and 5d-series metal cations are largerthan the and.
metals in the same group, there is less steric hindrance cations
among the ligands round the metal
therefore, less tendency for a given ligand to move from the coordination sphere. (ii) 4d-and Sd-series
metal cations are larger and use with ligands. Since
4d- and 5d-orbitals
4d- and 5d-orbitals are diffused (i.e., larger), in the
so these formation
orbitals extendoftowards bonds
sigma ligands andoverlap with
inthe
ligands orbitals more effectively and thus a difficulttobreak
rate determining step of strong M-L bond is formed and it is
dissociative reaction.
 Stabilityof Complexes and Reaction Mechanism
7.19
order of inertness of
Forexample, analogous complexes of group 9and 10is:
Co (IIl) <Rh (IIl) <Ir (III)
(Group 9)
Ni(I1) < Pd (II) < Pt(I).
(Group 10)
that Cuy 2+ta)
Itisto be
noted
significantgainin1 CFSE on going from
andCr(d)hydrated complexes have +2 charges and there is
octahedral to intermediate. These complexes have fastest water
molecules above and belowthe square plane are far apart from the Cu
water
exchange because two
as comparedto other four water molecules. Therefore, thesetwo water molecules above and belowion
the
rapidly.
squareplane react
Other Factors Affecting the Lability of a Complex
()Geometry of the Complex : The complexes of C.N. 4 undergo substitution reactions more
rapidly than analogous compounds of C.N.6. For example, [Ni(CN)4] give exchangereaction with
hCN more rapidly than [Mn(CN)6] and [Co (CN)6] complexes. The greater lability of square
nlanar complex,[Ni(CN)4J" is due to the reason that there is enough room round the metal cation for
the entry of incoming ligand intothe coordination sphere to form activated complex. This fifth ligand
enhances the rate of removal of one of the four ligands already present in the coordination sphere.
(2) Oxidation State of Central Metal Cation : Higher the oxidation state of central metal cation,
lower will the lability of the complex.
For example: +6
+3 +4 +5
)[AIF6J >(Si Fo 1 >[P F6J >[S+3F6] Order of lability
+1 +2
(ü) [Na(H,0)6J* >[Mg (H,0)61* >[Al(H,0)61*
increases with increase in ionic radius. For example
(3) lonic Radius : Lability of complex
(Sr(H,0)6j+ >[Ca(H,0)* >[Mg(H;0)%j*
DISSOCIATIVE(SN') MECHANISM
EVIDENCE FOR complexes is dissociative
mechanism for substitution reactions in octahedral
substitution but are much less
emost preferred are also possible in octahedral
mechanism. However associative reactions
the dissociative mechanism are :
Common. Some evidence which support
()the rate of exchange of water molecules.
(2) anation reactions.
(3) aquation or hydrolysis reactions.
(1) Water Exchange labeled bulk
are exchanged with isotopically
coordination sphere
When water molecules in the
water (H,0), the water exchange.
process is called +H,0
H,0ls[M(H,0);(H,0
[M(H,0)6 "t +