Chemistry Reference
In-Depth Information
Co
2
(CO)
8
+
OC
CO
(OC)
3
Co
Co
TS1
(OC)
3
Co
Co(CO)
3
CO
OC
CO
H
H
(OC)
3
Co
Co
A
O
(OC)
3
Co
Co(CO)
3
(OC)
3
Co
Co(CO)
2
O
H
H
TS2a
H
B
Reductive elimination
TS3a
or
b
O
CO
CO
(OC)
3
Co
Co(CO)
3
OC
(OC)
3
Co
Co
O
CO
O
(OC)
3
Co
Co(CO)
3
(OC)
3
Co
Co
Ga
TS2b
Gb
H
H
C
(OC)
3
Co
Co(CO)
3
Alkene insertion
TS1
O
(OC)
3
Co
Co(CO)
2
CO
O
O
(OC)
3
Co
Co(CO)
2
TS3a
Fa
(OC)
3
Co
Co(CO)
2
Fb
CO insertion
TS2a
or
b
D
O
(OC)
3
Co
Co(CO)
2
(OC)
3
Co
Co(CO)
3
CO
E
TS3b
Scheme 2.17
Detailed catalytic cycle of the PKR as defined by Nakamura and Yamanaka.
16a
The same nomenclature will be used throughout this section.
TS1
OC
40
B
CO
(OC)
3
Co
Co(CO)
3
+39.0
(+36.2)
(OC)
3
Co
Co
O
+36.4
(+31.2)
O
D
(OC)
3
Co
Co(CO)
3
C
+25.7
O
TS3a
+24.6
(+21.6)
TS2a
OC
CO
TS2b
(OC)
3
Co
Co
Ga
+8.1
(+10.5)
A
+10.0
(+6.9)
TS3b
-1.2
(+5.3)
TS1
Reagents
TS2a
OC
0
Fb
CO
+3.9
(+6.1)
0.0
(0.0)
E
-5.4
(OC)
3
Co
Co
Gb
-4.8
(-3.9)
-15.9
(-10.8)
Fa
HH
-6.8
C
TS3a
(OC)
3
Co
Co(CO)
3
-13.9
(-18.6)
Ga
(OC)
3
Co
Co(CO)
3
-17.4
(-12.7)
H
H
A
H
-40
-40.8
Figure 2.3
Reaction profile of the PK reaction at the B3LYP/631LAN level. The values in
parentheses are for B3LYP/6311SDD//B3LYP/631LAN.
