Monday May 31 IN6 Salon A

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Monday May 31 IN6 Salon A Organometallics in
Catalysis (joint with OR5) Organizer - W. Tam, D.
Zargarian Chair - W. Tam
1410 -1430 00459 A Combined Static and
Dynamic Density Functional Theory Approach to
Elementary Reaction Steps in Homogeneous
Catalysis Ziegler T., Margl P., Woo T.K., Schmid
R. Minserk Cheong Hazel Cox.
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Thermodynamics of addition reactions
Kkcal/mol
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Thermodynamics of addition reactions
Kcal/mol
Experimentally Rh endergonic and Ir exergonic
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Rh
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Ir
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b


b

M
e
ta
l
H
S
G
D
D
D
298
298
298
R
h
19.2
-21.1
25.5
a

a

a
(12.0
)
(
-
39.5)
(23.7
)
I
r
12.1
-23.4
19.1
a Experiment
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Rh
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Rh
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Experimental Insertion Barriers
Activation Parameters for the migratory CO
insertion in IrL(CO)2I2Men-
Activation Parameters for the migratory CO
insertion in RhL(CO)2I2Men-
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Reaction Energetics for Migratory Insertion of
M(CO)2I3Me-
Ir(CO)2I3Me- ? Ir(CO)I3(COMe)-




D
H


1
5
5
4
k
J
/
m
ol
D
H


1
3
0.
8
k
J
/m
o
l
e
x
p
t
t
h
e
o
r




S


9
1
8

J/
m
ol
K
S


8.
4
5

J/
m
ol
K
D

D

e
x
p
t
t
h
e
o
r




G


1
2
8
4
k
J
/
m
ol
G


1
2
8.
3 kJ/mol
D
D
2
9
8
,
e
x
p
t
2
9
8
,th
eo
r
Rh(CO)2I3Me- ? Rh(CO)I3(COMe)-
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2.90
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2.90
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Experimental Insertion Barriers
Activation Parameters for the migratory CO
insertion in IrL(CO)2I2Men-
Activation Parameters for the migratory CO
insertion in RhL(CO)2I2Men-
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