Reactions of Metal Complexes

Substitution reactions

MLn + L' MLn-1L' + L

Labile complexes <==> Fast substitution reactions (< few min)

Inert complexes <==> Slow substitution reactions (>h)
a kinetic concept

Not to be confused with

stable and unstable (a thermodynamic concept DGf <0)

Inert Intermediate Labile

d3, low spin d4-d6& d8 d8 (high spin) d1, d2, high spin d4-d6& d7-d10
low spin
 Mechanisms of ligand exchange reactions
in octahedral complexes
ML n X + Y ML n Y + X

Dissociative (D) Associative (A)

ML n X ML n Y ML n X ML n Y

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

For [Y] >> [ML5X]

Kinetics of associative reactions
Principal mechanisms of ligand exchange in octahedral complexes

Dissociative

Associative
 Dissociative pathway
(5-coordinated intermediate)

MOST COMMON

Associative pathway
(7-coordinated intermediate)
Experimental evidence for dissociative mechanisms

Rate is independent of the nature of L

Experimental evidence for dissociative mechanisms

Rate is dependent on the nature of L

 Inert and labile complexes
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
 Labile or inert?
L
L L
M
L L

Ea
L
L L
L M
L L L L
M X
L L
X
DG

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

 Why are some configurations inert and some are labile?

Inert !
Substitution reactions in square-planar complexes
the trans effect

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

(the ability of T to labilize X)

Synthetic applications
of the trans effect
Mechanisms of ligand exchange reactions in square planar complexes

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)

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

+1e (reduction)

Very fast reactions (much faster than ligand exchange)

May involve ligand exchange or not

Very important in biological processes (metalloenzymes)

 Outer 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+

Reactions ca. 100 times faster

than ligand exchange A B "solvent cage"
(coordination spheres remain the same)

r = k [A][B]

Ea
Tunneling A + B
mechanism
A' + B'

DG
 Inner sphere mechanism

[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(m-Cl)ÇrII(H2O)6]4+

[CoIII(NH3)5(m-Cl)ÇrII(H2O)6]4+ [CoII(NH3)5(m-Cl)ÇrIII(H2O)6]4+

[CoII(NH3)5(m-Cl)ÇrIII(H2O)6]4+ [CoII(NH3)5(H2O)]2+ + [ÇrIII(H2O)5Cl]2+

[CoII(NH3)5(H2O)]2+ [Ço(H2O)6]2+ + 5NH4+

 Inner sphere mechanism

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

Reactions much faster

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

r = k’ [Ox-X][Red] k’ = (k1k3/k2 + k3) Tunneling

through bridge
mechanism
Ea
Ox-X + Red
Ox(H2O)- + Red-X+

DG