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Substitution reactions
X ML n Y Y X
ML n XY
Interchange (I)
ML n X ML n Y
Y X
[ML n]°
Ia if association X Y Id if dissociation
is more important is more important
Kinetics
of dissociative reactions
Fast equilibrium
K1 = k1/k-1
Kinetics
of interchange reactions
k2 << k-1
Dissociative
Associative
Dissociative pathway
(5-coordinated intermediate)
MOST COMMON
Associative pathway
(7-coordinated intermediate)
Experimental evidence for dissociative mechanisms
Ea
L
L L
L M
L L L L
M X
L L
X
DG
Inert !
Substitution reactions in square-planar complexes
the trans effect
L X L Y
+X, -Y
M M
T L T L
L L S
M +S
L X L L
M
+Y L X
-X
Y
L L L L
M -d[ML3X]/dt = (ks + ky [Y]) [ML3X] M
L X L S
+Y
Y
L L
-X M
L S
L L
M -S
L Y
Electron transfer (redox) reactions
-1e (oxidation)
+1e (reduction)
r = k [A][B]
Ea
Tunneling A + B
mechanism
A' + B'
DG
Inner sphere mechanism
[Co(NH3)5Cl)]2+:::[Çr(H2O)6]2+ [CoIII(NH3)5(m-Cl)ÇrII(H2O)6]4+
[CoIII(NH3)5(m-Cl)ÇrII(H2O)6]4+ [CoII(NH3)5(m-Cl)ÇrIII(H2O)6]4+
k1 k3
Ox-X + Red Ox-X-Red Ox(H2O)- + Red-X+
k2 k4
DG