10/23/2015

Substitution reactions

MLn + L' MLn-1L' + L

Chapter 6
Labile complexes <==> Fast substitution reactions (< few min)
Reactions of Complexes Inert complexes <==> Slow substitution reactions (>h)
a kinetic concept
a kinetic

Lecturer: Not to be confused with stable and unstable (a 
thermodynamic concept DGf < 0)
Prof. Daud K. Walanda
Inert Intermediate Labile
d3, low spin d4-d6& d8 d8 (high spin) d1, d2, low spin d4-d6& d7-d10

Mechanisms of ligand exchange reactions
in octahedral complexes
MLn X + Y MLn Y + X

Dissociative (D) Associative (A)
MLn X MLn Y MLn X MLn Y

Y X
X MLn Y MLn XY

Interchange (I)
MLn X MLn Y

Y X
[MLn]°
Ia if association X Y Id if dissociation
is more important is more important

Fast equilibrium
Kinetics of dissociative  Kinetics of interchange  K1 = k1/k‐1

reactions reactions
k2 << k‐1

For [Y]  >> [ML5X]

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Principal mechanisms of ligand exchange in octahedral complexes

Kinetics of associative reactions

Dissociative
k1
ML5 X ML5 + X
slow r = k 1 [ML5X]
+Y k2
ML5 Y
fast

Associative
k1
ML5 X + Y ML5 XY
slow r = k 1 [ML5X][Y]
-X k2
ML5 Y
fast

Experimental evidence for dissociative mechanisms

Dissociative pathway
(5-coordinated intermediate)

MOST COMMON

Associative pathway
(7-coordinated intermediate)

Rate is independent of the nature of L

Inert and labile complexes

Experimental evidence for dissociative mechanisms Some common thermodynamic and kinetic profiles

Exothermic Exothermic Endothermic

(favored, large K) (favored, large K) (disfavored, small K)
Large Ea, slow reaction Large Ea, slow reaction Small Ea, fast reaction
Stable intermediate

Rate is dependent on the nature of L

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Labile or inert? Why are some configurations inert and some are labile?

L
L L
M
L L

Ea Inert !
L
L L
L M
L L L L
M X
L L
X G

LFAE = LFSE(sq pyr) - LFSE(oct)

Substitution reactions in square-planar complexes

Synthetic applications
the trans effect of the trans effect

L X L Y
+X, -Y
M M
T L T L

(the ability of T to labilize X)

Mechanisms of ligand exchange reactions in square planar complexes

Electron transfer (redox) reactions

L L S
M +S
L X L L
M -1e (oxidation)
+Y L X

-X
Y M1(x+)Ln + M2(y+)L’n M1(x +1)+Ln + M2(y-1)+L’n

L L L L
M -d[ML 3X]/dt = (ks + ky [Y]) [ML3X] M
L X +1e (reduction)
L S
+Y

Y Very fast reactions (much faster than ligand exchange)

L L
-X M May involve ligand exchange or not
L S
L L Very important in biological processes (metalloenzymes)
M -S
L Y

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Outer sphere mechanism

Inner sphere mechanism

[Fe(CN)6]4- + [IrCl6]2- [Fe(CN)6]3- + [IrCl6]3-

[Co(NH3)5Cl]2+ + [Ru(NH3)6]2+ [Co(NH3)5Cl]+ + [Ru(NH3)6]3+ [Co(NH3)5Cl)]2+ + [Çr(H2O)6]2+ [Co(NH3)5Cl)]2+:::[Çr(H2O)6]2+

[Co(NH3)5Cl)]2+:::[Çr(H2O)6]2+ [CoIII(NH3)5(-Cl)ÇrII(H2O)6]4+
Reactions ca. 100 times faster
than ligand exchange A B "solvent
solvent cage
cage"
(coordination spheres remain the same) [CoII(NH3)5(-Cl)ÇrIII(H2O)6]4+
[CoIII(NH3)5(-Cl)ÇrII(H2O)6]4+

r = k [A][B]
[CoII(NH3)5(-Cl)ÇrIII(H2O)6]4+ [CoII(NH3)5(H2O)]2+ + [ÇrIII(H2O)5Cl]2+
Ea
Tunneling A + B
mechanism
A' + B'
[CoII(NH3)5(H2O)]2+ [Ço(H2O)6]2+ + 5NH4+

G

Inner sphere mechanism

k1 k3
Ox-X + Red Ox-X-Red Ox(H2O)- + Red-X+
k2 k4

Reactions much faster

p
than outer sphere electron transfer
(bridging ligand often exchanged) Ox-X-Red

Tunneling
r = k’ [Ox-X][Red] k’ = (k1k3/k2 + k3)
through bridge
mechanism
Ea
Ox-X + Red
Ox(H2O)- + Red-X+

G