1

Prof. Dr. Usama El-Ayaan

 There are two limiting mechanisms

for substitution reactions of
coordination complexes,
associative, which corresponds to
the SN2 reaction in organic
chemistry, and
dissociative, which corresponds to
the SN1 reaction in organic
chemistry.
2

Prof. Dr. Usama El-Ayaan

Prof. Dr. Usama El-Ayaan

Mechanisms of ligand exchange reactions

in octahedral complexes
MLnY + X

MLnX + Y
Dissociative (D)
M Ln Y

M Ln X

Associative (A)

M Ln

M Ln Y

M Ln X
Y

M Ln XY

Interchange (I)
M Ln X

M Ln Y

Ia if association
is more important

[M Ln]
X

Prof. Dr. Usama El-Ayaan

Id if dissociation
is more important

Prof. Dr. Usama El-Ayaan

Associative Reactions
In the limiting case of an associative reaction the entering ligand
begins to interact with the metal as the bond to the departing ligand
(leaving group) lengthens. In order for the entering ligand to bond
to the metal there must be a vacant (preferably) or partially vacant
orbital that is accessible to the entering ligand. In an octahedral
complex only the t2g d orbitals are accessible as the eg orbitals and
the n+1 s and p orbitals are blocked by the presence of the original
six ligands. Associative processes are more likely for larger metal
ions than for smaller so that they are more important early in a
transition series and for heavier members of a family.

Prof. Dr. Usama El-Ayaan

Dissociative Reactions
In the limiting case the dissociative process
involves the formation of a five coordinate
intermediate as a result of complete bond
dissociation to the departing ligand (leaving
group). The five-coordinate intermediate then
reacts with the new ligand (entering group)
to reform a six-coordinate complex.
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Prof. Dr. Usama El-Ayaan

Principal mechanisms of ligand exchange in octahedral complexes

Dissociative

Associative

Prof. Dr. Usama El-Ayaan

Dissociative pathway
(5-coordinated intermediate)

MOST COMMON

Associative pathway
(7-coordinated intermediate)

Prof. Dr. Usama El-Ayaan

Inert and labile complexes

Some common thermodynamic and kinetic profiles

Exothermic
(favored, large K)
Large Ea, slow reaction

Exothermic
(favored, large K)
Large Ea, slow reaction
Stable intermediate
Prof. Dr. Usama El-Ayaan

Endothermic
(disfavored, small K)
Small Ea, fast reaction

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Experimental evidence for dissociative mechanisms

Rate is independent of the nature of L

Prof. Dr. Usama El-Ayaan

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Experimental evidence for dissociative mechanisms

Rate is dependent
on the nature of L
Prof. Dr. Usama El-Ayaan

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13

Prof. Dr. Usama El-Ayaan

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Prof. Dr. Usama El-Ayaan

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Prof. Dr. Usama El-Ayaan

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Prof. Dr. Usama El-Ayaan

:
- L
-
- -

Prof. Dr. Usama El-Ayaan

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Experimental evidence for dissociative mechanisms

Rate is independent of the nature of L

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Prof. Dr. Usama El-Ayaan

Experimental evidence for dissociative mechanisms

Rate is dependent on the nature of L

Prof. Dr. Usama El-Ayaan

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Ru-OH2

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Prof. Dr. Usama El-Ayaan

Prof. Dr. Usama El-Ayaan

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-
-
-

22

X

-

Prof. Dr. Usama El-Ayaan


Trans-[Co(N4)Cl2]+ + H2O Trans-[Co(N4)Cl(H2O)]2+ + Cl ) (N4 Me6-cyclam .cyclam

Me6-cyclam

cyclam

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Prof. Dr. Usama El-Ayaan

Prof. Dr. Usama El-Ayaan

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Steric effect
(1) trans-[CoCl2(en)2]+ + H2O

trans-[CoCl (H2O)(en)2]2+ + Cl-

K = 3.2 x 10-5

(2) trans-[CoCl2(Me4en)2]+ + H2O

trans-[CoCl (H2O)(Me4en)2]2+ + Cl-

K = 3.2 x 10-2

Prof. Dr. Usama El-Ayaan

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 1000

()D
( )

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Prof. Dr. Usama El-Ayaan

Stereochemistry of substitution

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Prof. Dr. Usama El-Ayaan

Coordination # : 6 [5] - 6

Intermediate

Remember

Square pyramid
Prof. Dr. Usama El-Ayaan

Trigonal bipyramid
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Prof. Dr. Usama El-Ayaan

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Prof. Dr. Usama El-Ayaan

 )(hydrolysis

trans-[Co(en)2ClA]+

cis-[Co(en)2ClA]+
cis- trans-

( )A trans
( )p

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Prof. Dr. Usama El-Ayaan

Prof. Dr. Usama El-Ayaan

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33

Prof. Dr. Usama El-Ayaan

Base catalyzed hydrolysis

Werner


[CoCl(NH3)5]2+ + HO- [Co(OH)(NH3)5]2+ + Cl-

NHR2

H 2O

Co

NR2

Co

k2

NR2
Co

-X

OH

k1
OH-

]1 + k1 [OH-

Co
X

]k2k1[OH-

NHR2

= kobs

Prof. Dr. Usama El-Ayaan

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conjugate base
( )
.)dissociative conjugate base( Dcb

Presence of acidic protons

.Dcb

[Co(CN)5Cl]3 -trans-[CoCl2(Ph2PCH2CH2PPh2)2]+ .Prof. Dr. Usama El-Ayaan

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Stereochemistry of base hydrolysis reactions

OH
N

OH
N

N
Co

93%

Co

X
N
1
N
N

OH

Co

OH

N
OH

N
2

Co
X

OH
Co
OH

7%

Product distribution is independent of the leaving group and the isomeric form of
the starting material.
This behavior is not only consistent with the dissociative mechanism, but also
indicative of a trigonal bipyramidal intermediate
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Prof. Dr. Usama El-Ayaan

Acid catalyzed hydrolysis

:
.
.1
.
.2
.
.3

Protonation of the leaving group

.conjugate base of relatively weak acid
.

]+

[CoX2en2 , If X= Cl, Br, I

( )HCl, HBr and HI .

Prof. Dr. Usama El-Ayaan

37

For X=F , the substitution is strongly acid catalyzed because of much weaker acidity
of HF in water.
X = F HF

2+

2+

N
F
Co
OH2

N
N

F
Co
-HF

N
N

H+

FH
N

F
Co
F

N
N

HF
.
HF .F-

Prof. Dr. Usama El-Ayaan

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 :
-.
L

L
L

OH

- CO2
L

O
H C

H+

M
L

L
M

L
O

:
Cl
Cl

P
PH

Fe
Cl

Cl
P

H+

Fe
P

P
Cl

Cl
P

P
Fe
P
Cl

P
Fe
P
Cl

.
Prof. Dr. Usama El-Ayaan
.

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)trans-[M(O)(OH)(CN)4]2- (M = Mo, W, Tc or Re
S
C
N

2CN

NC

M
NC

CN
O

NCS

CN

NC

H2O

NC

CN
O

OH2

CN

2NC

M
CN
O

NC

OH
NC

CN
M

NC

CN
O

.
.

Prof. Dr. Usama El-Ayaan

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Protonation of non-labile ligand

.
)cis-[M(N2)2(PMePh)4] (M = Mo or W

H

2+

N
OMe

H
OMe

R3P

M
PR3

MeOH

R3P

R3P

PR3
HOMe

N2

R3P

M
2H

OMe

2+

PR3

R3P
2H

M
PR3

N2

R3P

PR3

R3P

M
PR3

R3P

( )
N2 .PR3
d

Prof. Dr. Usama El-Ayaan

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 .

.

Protonation at the metal

.
] [Fe(CO)5 [FeH(CO)5]+
.

.
] [Fe(CO)5 [Fe(CO)5]+ .

Prof. Dr. Usama El-Ayaan

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