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Journal of the American Chemical Society
Table 2. Comparative Propylene Metathesis Results for the Molybdenum Catalysts: Activity (Cumulated TON) and Product
Selectivity after 25 h of Reaction in a Dynamic Flow Reactor at 30 °C.
1
2
3
4
5
TOFa
TONb
Product selectivity [%]c
Precatalyst
at (60 min)
102.1
(after 25 h)
89260
ethylene
50.0
E-2-butene Z-2-butene Z/E
t
( SiO)MoO(CH2 Bu)3 1/SiO2-700
30.9
19.1
0.62
6
7
t
( SiO)Mo(=NAr)(=CHtBu)(CH2 Bu)
2/SiO2-700
26.2
6710
50.0
21.4
28.6
1.33
8
9
t
( SiO)WO(CH2 Bu)3 3/SiO2-700
5.6
4.9
0.5
2960
6000
250
50.0
50.0
50.0
23.1
32.3
25.4
26.9
17.7
24.6
1.16
0.55
0.96
t
d
( SiO)WO(CH2 Bu)3 3/SiO2-700
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
e
MoO3/SiO2
c
aTOF is expressed in mol of propylene transformed/mol of metal/min. bTON is expressed in mol of propylene transformed/mol of metal. Selectivities are defined as the molar
amount of product over the total molar amount of products, at the end of the reaction (1500 min). reaction performed at 80 °C, 20 ml min-1, (R = 60 molC3H6 molMo min−1).
d
−1
e
reaction performed at 30 °C, 10 ml/min (R = 17.5 molC3H6 molMo−1 min−1
)
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
Experimental procedures
Molybdenum K-edge k3-weighted EXAFS
Molar selectivities.
Corresponding Author
N.M. nicolas.merle@univ-lyon1.fr
M. T. mostafa.taoufik@univ-lyon1.fr
R.M.G. regis.gauvin@ensc-lille.fr
J.M.B. jeanmarie.basset@kaust.edu.sa
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
The Competitive Research Grant Program, supported by the
KAUST Research Fund (project # 2174 CGR3) and the Agence
Nationale de la Recherche (ANR-12-BS07-0021-01, OXOCAT)
are gratefully acknowledged for their financial support. We would
like to thank Olivier Mathon for his help during the recording of
the XAS spectra on BM23 beam-line at ESRF (experiment code
IN-986).
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REFERENCES
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