Table 4
Ir-catalyzed dehydrogenation of formic acid
Entry
Catalyst
Solvent
Additives
Temp (
C)
Time
TON
TOF (h
À1
)
Ref
1
[IrH
3 (PPh
3 )
3 ]
C H
3 CO
2 H
–
Reflux
1 h
8,889
a
8,889
[143]
2
76
H
2 O
–
90
N.A.
N.A.
14,000
[150]
3
b
77
H
2 O
–
23
30 h
>500
>17
a
[151]
4
78
H
2 O
–
90
4.5 h
30,000
6,667
a
[152]
5
79
H
2 O
–
60
24 h
33,000
1,375
a
[153]
6
80
H
2 O
–
60
2,600 h
5,000,000
1,923
a
[154]
7
81
H
2 O
HCO
2 Na
80
5 min
3,292
a
39,500
[152]
8
82
H
2 O
HCO
2 Na
80
12 h
308,000
25,667
a
[155]
9
83
H
2 O
–
80
14 h
2,400,000
171,429
a
[156]
10
84
H
2 O
HCO
2 Na
90
N.A.
N.A.
144,000
[157]
11
85
H
2 O
–
90
10 min
47,000
282,000
a
[156]
12
86
H
2 O
–
100
4.8 h
90,000
18,750
a
[158]
13
87
H
2 O
–
80
10 min
5,667
a
34,000
[159]
14
88
H
2 O
–
50
363 h
2,000,000
5,510
a
[160]
15
89
H
2 O
–
60
2.5 h
40,000
16,000
a
[161]
16
90
H
2 O
HCO
2 Na
100
10 min
53,666
a
322,000
[162]
17
91
H
2 O
–
60
580 h
2,050,000
3,534
a
[162]
18
92
H
2 O
–
70
35 days
10,000,000
11,905
a
[163]
19
35
H
2 O
–
80
10 days
710,000
2,958
a
[164]
20
93
–
Et
3 N
40
2 h
6,680
a
3,340
[165]
21
94
H
2 O
HCO
2 Na
90
2 min
3,333
a
100,000
[166]
22
95
H
2 O
HCO
2 Na
50
100 h
1,000,000
10,000
a
[167, 168]
23
96
H
2 O
HCO
2 K
25
N.A.
14,400
N.A.
[169]
24
97
H
2 O
HCO
2 Na
100
1 h
2,826
2,826
[170]
25
98
H
2 O
–
70
175 h
5,020,000
28,686
a
[171]
26
99
DME/H
2 O
–
35
1 h
2,570
2,570
a
[172]
44
T. Shimbayashi and K. Fujita