inorganic chemistry

TABLE IV

T

HERMODYNAMIC

D

ATA FOR THE

P

HOTOCHEMICAL

L

IGAND

SUBSTITUTION

R

EACTIONS OF

[Re(X

bpy)(CO) 2

(PR 3

)] 3

þ

(^3

)

IN

CH

CN. 3

[Re(X

bpy)(CO) 2

(PR 3

)] 3

þ

E

00

(^3) (
MLCT)
a
(cm


1 )
kd
(10
5

s
1 )
D
G
6¼^298
b
(cm


1 )(
E
00
þ
D
G
6¼)
298
(cm


1 )
X
PR
3
3a
H
P(OEt)
3
19,470

55
6.9
3810

590
23,280

650
3b
CH
3
P(OEt)
3
19,637

50
4.1
3650

80
23,290

130
3c
CF
3
P(OEt)
3
17,272

49
60
4820

140
22,090

190
3d
H
P(
n-Bu)
3
18,672

50
11
3480

830
22,150

880
3e
H
PEt
3
18,649

51
11
3390

610
22,030

660
3f
H
PPh
3
19,000

31
8.5
3230

1650
22,230

1680
3g
H
P(OMe)Ph
2
19,553

46
9.7
3240

440
22,790

490
3h
H
P(O
i-Pr)
3
19,239

52
7.9
3610

760
22,840

810
3i
H
P(OMe)
3
19,678

43
6.2
3740

760
23,420

800
a^0

• 0 band energy gap between the

3 MLCT and the ground states.

bFree activation energy change at 298 K.