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V.SANTHANAM
Department of Chemistry
SCSVMV
 Complexes in which exchange of one or
more ligands are rapidly exchanged are
called labile complexes.
 If the rate of ligand exchange is slow then
the complex is said to be inert.
 Lability is not related to the thermodynamic
stability of a complex.
 A stable complex may be labile or inert , so
as the unstable complex .
 [Cu(NH3)4(H2O2)2]2+
is labile. Its aqueous
solution is blue in color.
 When concentrated hydrochloric acid is
added to this solution, the blue solution
immediately turns green ,giving [CuCl4]2-
.
 But when the complex is kept as such it
remains as such with out any decomposition
(i.e stable)
 [Co(NH3)6]3+
reacts slowly. When this complex
is treated with concentrated HCl, no reaction
takes place. Only when it is heated with 6M
HCl for many hours, one NH3 is substituted by
Cl-
.
[Co(NH3)6]3+
+ HCl [Co(NH3)5Cl]2+
+ NH4
+
 Size of the central metal ion
Smaller the size of the metal ion, greater will be the
inertness because the ligands are held tightly by
the metal ion.
 Charge on the central metal ion
Greater the charge on the metal ion, greater will be
the inertness of the complex. Since the M-L bonds
are stronger.
 d-electron configuration
 If electrons are present in the antibonding eg
*
orbitals,
the complex will be labile -the ligands will be weakly
bonded to the metal and hence can be substituted
easily.
 Complexes with empty t2g orbitals, will be labile
because ligands can approach easily without much
repulsion.
 In short, if the complex contains less than three d-
electrons, it will be labile. Or, if one or more eg
*
electrons are present, it will be labile
No. of d electrons
& electron configuration
Nature Example
d0 Labile [CaEDTA]2-
d1
; t2g
1
eg
0
Labile [Ti(H2O)6]3+
d2
; t2g
2
eg
0
Labile [V(phen)3]3+
d3
; t2g
3
eg
0
Inert [V(H2O)6] 3+
d4
(high-spin); t2g
3
eg
1
Labile [Cr(H2O)6]3+
d4
(low-spin); t2g
4
eg
0
Inert [Cr(CN)6]4-
d5
(high-spin); t2g
3
eg
2
Labile [Mn(H2O)6]2+
d5
(low-spin); t2g
5
eg
0
Inert [Mn(CN)6]4-
d6
(high-spin); t2g
4
eg
2
Inert [Mn(H2O)6]2+
d6
(low-spin); t2g
6
eg
0
Inert [Fe(CN)6]4-
d7
, d8
, d9
, d10 Labile
 CFT assumes the splitting of d orbitals of metal.
 Filling of e-
s in them results in different CFSE.
 CFAE – Crystal Field Activation Energy
CFAE = CFSE of intermediate – CFSE of Reactant
 Since the geometries of the reactant and intermediate
are different their splitting and CFSE are also different.
 If the calculated CFAE is negative or zero or low
the reacting complex will require less energy to
form the intermediate, hence it will be labile.
 If CFAE is a high positive value then the complex
will be inert.
 It must be borne in mind that CFAE is only a part
of actual AE and other factors are also operative.
 The geometry of the complex is assumed to
be Oh even if all the ligands are not identical.
 The inter electronic repulsions are neglected.
 The Dq values of the reactant and
intermediate are assumed to be same.
 The Jahn-Teller effect is not affecting CFSE.
 Because of the drastic assumptions made,
some of the CFAE values are –ive.
 However when calculated with proper
attention to all effects, CFAE is always +ive.
 CFAE can be small or zero but never –ive
 By oversimplified approach the –ive values of
CFAE may be taken as zero.
 Substitution of ligands
 Solvolysis
 Anation
 Reactions of coordinated ligands
 Racemization
 Electron transfer reactions
 Photo chemical reactions
• Ligand displacements are nucleophilic
substitution reactions.
• Rate is governed by ligand
nucleophilicity
The rate of attack on a complex by a
given ligand relative to the rate of attack
by a reference base.
8
Three types of ligands are present
– Entering Ligand: Y
– Leaving Ligand: X
– Spectator Ligand
• Species that neither enters nor leaves
• Particularly important when located in a Trans
position, designated T
Dissociative: One of the ligands
dissociates from the reactant, to form a
reaction intermediate with lower
coordination number than reactants
or products
• Octahedral complexes and smaller metal centers
• Rates depend on leaving group
SYSTE
M
Weak Field / High Spin Strong Field / Low Spin
Oh SP CFAE Oh SP CFAE
d0
0 0 0 0 0 0
d1
-4 -4.57 -0.57 -4 -4.57 -0.57
d2
-8 -9.14 -1.14 -8 -9.17-4 -1.14
d3
-12 -10.00 2.00 -12 -10.00 2.00
d4
-6 -9.14 -3.14 -16 -14.57 1.43
d5
0 0 0 -20 -19.14 0.86
d6
-4 -4.57 -0.57 -24 -20.00 4.00
d7
-8 -9.14 -1.14 -18 -19.14 -1.14
d8
-12 -10.00 2.00 -12 -10.00 2.00
d9
-6 -9.14 -3.14 -6 -9.14 -3.14
d10
0 0 0 0 0 0
Associative: reaction intermediate is
formed by including the incoming
ligand in the coordination sphere
and has higher coordination
number than reactants or products
• Lower coordination number
complexes
• Rates depend on the entering group
SYSTE
M
Weak Field / High Spin Strong Field / Low Spin
Oh OW CFAE Oh OW CFAE
d0
0 0 0 0 0 0
d1
-4 -6.08 -2.08 -4 -6.08 -2.08
d2
-8 -8.68 -0.68 -8 -8.68 -0.68
d3
-12 -10.20 1.80 -12 -10.20 1.80
d4
-6 -8.79 -2.79 -16 -16.26 -0.26
D5
0 0 0 -20 -18.86 1.14
d6
-4 -6.08 -2.08 -24 -20.37 3.63
d7
-8 -8.68 -0.68 -18 -18.98 -0.98
d8
-12 -10.20 1.80 -12 -10.20 1.80
d9
-6 -8.79 -2.79 -6 -8.79 -2.79
d10
0 0 0 0 0 0
 It is a continuous single step
process
 Two types exist
 Interchange associative (IA ) –
Bond making more important
 Interchange dissociative (ID) –
Bond breaking more important
 Ammine complexes of Co(III) are the most
studied.
 Water is the medium of reaction.
 Usually replacement of NH3 derivatives is
very slow, so only other ligands are
considered.
[Co(NH3)5X]2+
+ H2O  [Co(NH3)5(H2O)]3+
+ X-
 Rate = k. [Co(NH3)5X]2+
. [H2O]
 Rate = k’. [Co(NH3)5X]2+
 Charge on the complex
 Steric factors
 Effect of leaving group
 Effect of solvent
 Presence of pi-donors and acceptors as
spectator ligands
 The increase in positive charge decreases the rate
of reaction following a dissociative mechanism
because the breaking the metal-ligand bond
becomes difficult.
For aquation of the Ru complexes the trend is as
shown
[RuCl6]3-
1.0 s-1
[RuCl3(H2O)3]0
2.1 x 10-6
s-
1
Complex Rate constant S-1
[Co(NH3)5(NO3)]2+
~ 10-5
[Co(NH3)5I]2+
~ 10-6
[Co(NH3)5F]2+
~ 10-8
Thus it is proved that M-X bond
breaking is very much important
in aquation reactions than bond
formation.
 The rate of aquation of [Co(NH3)5X]2+
depends on the
stability of M-X bond.
 If the M-X bond is more stable rate of reaction is
low.
 The order of reactivity is
HCO3
-
>NO3
-
>I-
>Br-
>Cl-
>SO4
2-
> F-
>SCN-
>NO2
-
 This is the order of decreasing thermodynamic
stability of the complexes formed with these groups
 Anation reactions do not depend very much on the
nature of the entering group, Y-
.
 Instead, it is very much dependent on the nature of the
bond being broken.
 Experimental data show that the rate is of the order 10-6
for the different entering groups (Y-
), N3
-
, SO4
2-
, Cl-
or
NCS-
clearly indicating that the rate is independent of the
nature of the entering group
 Another important experimental support for
this observation is that ligand exchange
reactions do not take place directly but
instead takes place through aquation and
then anation.
[Co(NH3)5X]2+
+ Y-
[Co(NH3)5Y]2+
+ X-
 This indicates that the Co-X bond breaking is very much
significant and then whatever species is present at a higher
concentration will add in anation reaction. Thus, nature of Y-
 When the non-leaving ligands are bulky, they will be
crowding the central metal ion.
 The incoming ligand will find it difficult to approach
the central metal ion slowing down the rate of
reaction taking place by associative mechanism.
 Instead, if the reaction takes place by dissociative
mechanism, the rate of the reaction will increase
because the crowding around the metal ion is
reduced.
• Steric crowding around the metal centre favors
dissociative activation
• Dissociative activation relieves crowding around
the complex
• Steric crowding has been qualitatively and
quantitatively explored
– Tolman Cone Angle
Complex k x 104
S-1
Complex k x 104
S-1
Cis-[Co(NH3)4Cl2]+
Very fast [Co(NH3)5Cl]2+
(0)
4.0
Cis-[Co(en)2Cl2]+
150 [Co(en)2(NH3)Cl]2+
(2)
0.85
Cis-[Co(trien)Cl2]+
90 [Co(tren)(NH3)Cl]2+
(3)
0.40
trans-[Co(NH3)4Cl2]+
1100 [Co(en)(dien)
(NH3)Cl]2+
(3) 0.31
trans-[Co(en)(NH3)2Cl2]+
130 [Co(tetren)Cl]2+
(4)
0.15
trans-[Co(en)2Cl2]+
19
AA k x 103
min-1
H2N-CH2-CH2-NH2 (en) 1.9
H2N-CH2-CH(CH3)-NH2 (pn) 3.7
H2N-CH(CH3)-CH(CH3)-NH2 (dl - bn) 8.8
H2N-CH(CH3)-CH(CH3)-NH2 (m – bn) 250
H2N-C(CH3)2-C(CH3)2-NH2 (tetrameen)
instantaneous
Reactions of complexes

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Reactions of complexes

  • 2.  Complexes in which exchange of one or more ligands are rapidly exchanged are called labile complexes.  If the rate of ligand exchange is slow then the complex is said to be inert.  Lability is not related to the thermodynamic stability of a complex.  A stable complex may be labile or inert , so as the unstable complex .
  • 3.  [Cu(NH3)4(H2O2)2]2+ is labile. Its aqueous solution is blue in color.  When concentrated hydrochloric acid is added to this solution, the blue solution immediately turns green ,giving [CuCl4]2- .  But when the complex is kept as such it remains as such with out any decomposition (i.e stable)
  • 4.  [Co(NH3)6]3+ reacts slowly. When this complex is treated with concentrated HCl, no reaction takes place. Only when it is heated with 6M HCl for many hours, one NH3 is substituted by Cl- . [Co(NH3)6]3+ + HCl [Co(NH3)5Cl]2+ + NH4 +
  • 5.  Size of the central metal ion Smaller the size of the metal ion, greater will be the inertness because the ligands are held tightly by the metal ion.  Charge on the central metal ion Greater the charge on the metal ion, greater will be the inertness of the complex. Since the M-L bonds are stronger.
  • 6.  d-electron configuration  If electrons are present in the antibonding eg * orbitals, the complex will be labile -the ligands will be weakly bonded to the metal and hence can be substituted easily.  Complexes with empty t2g orbitals, will be labile because ligands can approach easily without much repulsion.  In short, if the complex contains less than three d- electrons, it will be labile. Or, if one or more eg * electrons are present, it will be labile
  • 7. No. of d electrons & electron configuration Nature Example d0 Labile [CaEDTA]2- d1 ; t2g 1 eg 0 Labile [Ti(H2O)6]3+ d2 ; t2g 2 eg 0 Labile [V(phen)3]3+ d3 ; t2g 3 eg 0 Inert [V(H2O)6] 3+ d4 (high-spin); t2g 3 eg 1 Labile [Cr(H2O)6]3+ d4 (low-spin); t2g 4 eg 0 Inert [Cr(CN)6]4- d5 (high-spin); t2g 3 eg 2 Labile [Mn(H2O)6]2+ d5 (low-spin); t2g 5 eg 0 Inert [Mn(CN)6]4- d6 (high-spin); t2g 4 eg 2 Inert [Mn(H2O)6]2+ d6 (low-spin); t2g 6 eg 0 Inert [Fe(CN)6]4- d7 , d8 , d9 , d10 Labile
  • 8.  CFT assumes the splitting of d orbitals of metal.  Filling of e- s in them results in different CFSE.  CFAE – Crystal Field Activation Energy CFAE = CFSE of intermediate – CFSE of Reactant  Since the geometries of the reactant and intermediate are different their splitting and CFSE are also different.
  • 9.  If the calculated CFAE is negative or zero or low the reacting complex will require less energy to form the intermediate, hence it will be labile.  If CFAE is a high positive value then the complex will be inert.  It must be borne in mind that CFAE is only a part of actual AE and other factors are also operative.
  • 10.  The geometry of the complex is assumed to be Oh even if all the ligands are not identical.  The inter electronic repulsions are neglected.  The Dq values of the reactant and intermediate are assumed to be same.  The Jahn-Teller effect is not affecting CFSE.
  • 11.  Because of the drastic assumptions made, some of the CFAE values are –ive.  However when calculated with proper attention to all effects, CFAE is always +ive.  CFAE can be small or zero but never –ive  By oversimplified approach the –ive values of CFAE may be taken as zero.
  • 12.  Substitution of ligands  Solvolysis  Anation  Reactions of coordinated ligands  Racemization  Electron transfer reactions  Photo chemical reactions
  • 13. • Ligand displacements are nucleophilic substitution reactions. • Rate is governed by ligand nucleophilicity The rate of attack on a complex by a given ligand relative to the rate of attack by a reference base. 8
  • 14. Three types of ligands are present – Entering Ligand: Y – Leaving Ligand: X – Spectator Ligand • Species that neither enters nor leaves • Particularly important when located in a Trans position, designated T
  • 15.
  • 16. Dissociative: One of the ligands dissociates from the reactant, to form a reaction intermediate with lower coordination number than reactants or products • Octahedral complexes and smaller metal centers • Rates depend on leaving group
  • 17.
  • 18.
  • 19.
  • 20.
  • 21. SYSTE M Weak Field / High Spin Strong Field / Low Spin Oh SP CFAE Oh SP CFAE d0 0 0 0 0 0 0 d1 -4 -4.57 -0.57 -4 -4.57 -0.57 d2 -8 -9.14 -1.14 -8 -9.17-4 -1.14 d3 -12 -10.00 2.00 -12 -10.00 2.00 d4 -6 -9.14 -3.14 -16 -14.57 1.43 d5 0 0 0 -20 -19.14 0.86 d6 -4 -4.57 -0.57 -24 -20.00 4.00 d7 -8 -9.14 -1.14 -18 -19.14 -1.14 d8 -12 -10.00 2.00 -12 -10.00 2.00 d9 -6 -9.14 -3.14 -6 -9.14 -3.14 d10 0 0 0 0 0 0
  • 22. Associative: reaction intermediate is formed by including the incoming ligand in the coordination sphere and has higher coordination number than reactants or products • Lower coordination number complexes • Rates depend on the entering group
  • 23.
  • 24.
  • 25.
  • 26. SYSTE M Weak Field / High Spin Strong Field / Low Spin Oh OW CFAE Oh OW CFAE d0 0 0 0 0 0 0 d1 -4 -6.08 -2.08 -4 -6.08 -2.08 d2 -8 -8.68 -0.68 -8 -8.68 -0.68 d3 -12 -10.20 1.80 -12 -10.20 1.80 d4 -6 -8.79 -2.79 -16 -16.26 -0.26 D5 0 0 0 -20 -18.86 1.14 d6 -4 -6.08 -2.08 -24 -20.37 3.63 d7 -8 -8.68 -0.68 -18 -18.98 -0.98 d8 -12 -10.20 1.80 -12 -10.20 1.80 d9 -6 -8.79 -2.79 -6 -8.79 -2.79 d10 0 0 0 0 0 0
  • 27.
  • 28.
  • 29.
  • 30.
  • 31.
  • 32.
  • 33.  It is a continuous single step process  Two types exist  Interchange associative (IA ) – Bond making more important  Interchange dissociative (ID) – Bond breaking more important
  • 34.
  • 35.
  • 36.  Ammine complexes of Co(III) are the most studied.  Water is the medium of reaction.  Usually replacement of NH3 derivatives is very slow, so only other ligands are considered. [Co(NH3)5X]2+ + H2O  [Co(NH3)5(H2O)]3+ + X-  Rate = k. [Co(NH3)5X]2+ . [H2O]  Rate = k’. [Co(NH3)5X]2+
  • 37.  Charge on the complex  Steric factors  Effect of leaving group  Effect of solvent  Presence of pi-donors and acceptors as spectator ligands
  • 38.  The increase in positive charge decreases the rate of reaction following a dissociative mechanism because the breaking the metal-ligand bond becomes difficult. For aquation of the Ru complexes the trend is as shown [RuCl6]3- 1.0 s-1 [RuCl3(H2O)3]0 2.1 x 10-6 s- 1
  • 39. Complex Rate constant S-1 [Co(NH3)5(NO3)]2+ ~ 10-5 [Co(NH3)5I]2+ ~ 10-6 [Co(NH3)5F]2+ ~ 10-8 Thus it is proved that M-X bond breaking is very much important in aquation reactions than bond formation.
  • 40.  The rate of aquation of [Co(NH3)5X]2+ depends on the stability of M-X bond.  If the M-X bond is more stable rate of reaction is low.  The order of reactivity is HCO3 - >NO3 - >I- >Br- >Cl- >SO4 2- > F- >SCN- >NO2 -  This is the order of decreasing thermodynamic stability of the complexes formed with these groups
  • 41.  Anation reactions do not depend very much on the nature of the entering group, Y- .  Instead, it is very much dependent on the nature of the bond being broken.  Experimental data show that the rate is of the order 10-6 for the different entering groups (Y- ), N3 - , SO4 2- , Cl- or NCS- clearly indicating that the rate is independent of the nature of the entering group
  • 42.  Another important experimental support for this observation is that ligand exchange reactions do not take place directly but instead takes place through aquation and then anation. [Co(NH3)5X]2+ + Y- [Co(NH3)5Y]2+ + X-  This indicates that the Co-X bond breaking is very much significant and then whatever species is present at a higher concentration will add in anation reaction. Thus, nature of Y-
  • 43.  When the non-leaving ligands are bulky, they will be crowding the central metal ion.  The incoming ligand will find it difficult to approach the central metal ion slowing down the rate of reaction taking place by associative mechanism.  Instead, if the reaction takes place by dissociative mechanism, the rate of the reaction will increase because the crowding around the metal ion is reduced.
  • 44. • Steric crowding around the metal centre favors dissociative activation • Dissociative activation relieves crowding around the complex • Steric crowding has been qualitatively and quantitatively explored – Tolman Cone Angle
  • 45. Complex k x 104 S-1 Complex k x 104 S-1 Cis-[Co(NH3)4Cl2]+ Very fast [Co(NH3)5Cl]2+ (0) 4.0 Cis-[Co(en)2Cl2]+ 150 [Co(en)2(NH3)Cl]2+ (2) 0.85 Cis-[Co(trien)Cl2]+ 90 [Co(tren)(NH3)Cl]2+ (3) 0.40 trans-[Co(NH3)4Cl2]+ 1100 [Co(en)(dien) (NH3)Cl]2+ (3) 0.31 trans-[Co(en)(NH3)2Cl2]+ 130 [Co(tetren)Cl]2+ (4) 0.15 trans-[Co(en)2Cl2]+ 19
  • 46. AA k x 103 min-1 H2N-CH2-CH2-NH2 (en) 1.9 H2N-CH2-CH(CH3)-NH2 (pn) 3.7 H2N-CH(CH3)-CH(CH3)-NH2 (dl - bn) 8.8 H2N-CH(CH3)-CH(CH3)-NH2 (m – bn) 250 H2N-C(CH3)2-C(CH3)2-NH2 (tetrameen) instantaneous