Catalysis Science & Technology
Paper
was cooled and the gas phase trapped in liquid nitrogen in
order to record IR spectra. In parallel, the gas phase was
analyzed by expanding aliquots in a small volume for
injection in GC. Alkanes were titrated on a Hewlett-Packard
5890 series II gas chromatograph equipped with a flame
ionization detector and an Al2O3–KCl on fused silica column
(50 m × 0.32 mm).
4 C.-Y. Chen, D. J. O'Rear and S. R. Brundage, Chevron U.S.A.
Inc., Patent application, WO2002000578, 2002.
5 M. C. Haibach, S. Kundu, M. Brookhart and A. S. Goldman,
Acc. Chem. Res., 2012, 45, 947–958.
6 V. Vidal, A. Theolier, J. Thivolle-Cazat, J. M. Basset and
J. Corker, J. Am. Chem. Soc., 1996, 118, 4595–4602.
7 V. Vidal, A. Theolier, J. Thivolle-Cazat and J. M. Basset,
Science, 1997, 276, 99–102.
8 J.-M. Basset, C. Coperet, L. Lefort, B. M. Maunders,
O. Maury, E. Le Roux, G. Saggio, S. Soignier, D. Soulivong,
G. J. Sunley, M. Taoufik and J. Thivolle-Cazat, J. Am. Chem.
Soc., 2005, 127, 8604–8605.
9 J.-M. Basset, C. Coperet, D. Soulivong, M. Taoufik and
J. Thivolle-Cazat, Acc. Chem. Res., 2010, 43, 323–334.
10 N. Merle, F. Stoffelbach, M. Taoufik, E. Le Roux, J. Thivolle-
Cazat and J.-M. Basset, Chem. Commun., 2009, 2523–2525.
11 A. Garron, F. Stoffelbach, N. Merle, K. C. Szeto, J. Thivolle-
Cazat, J.-M. Basset, S. Norsic and M. Taoufik, Catal. Sci.
Technol., 2012, 2, 2453–2455.
12 V. Polshettiwar, J. Thivolle-Cazat, M. Taoufik, F. Stoffelbach,
S. Norsic and J.-M. Basset, Angew. Chem., Int. Ed., 2011, 50,
2747–2751.
13 O. Maury, L. Lefort, V. Vidal, J. Thivolle-Cazat and
J.-M. Basset, Angew. Chem., Int. Ed., 1999, 38, 1952–1955.
14 O. Maury, L. Lefort, V. Vidal, J. Thivolle-Cazat and
J.-M. Basset, Organometallics, 2010, 29, 6612–6614.
15 R. R. Schrock and J. D. Fellmann, J. Am. Chem. Soc.,
1978, 100, 3359–3370.
Metathesis of alkanes in a batch reactor
[(SiO)2Ta–H]/SiO2, 1, (300 mg; 5.95 wt% Ta) or [(SiO)2Ta–H]/
MCM-41, 2, (150 mg; 11.7 wt% Ta) were charged within a
glove-box into a glass reactor (500 ml). After evacuation of
argon, the reactor was filled again with ethane or propane
(0.8 bar) through a molecular sieve and deoxo-catalyst trap
then heated to 150 °C in an oven. The reaction products were
analyzed periodically by GC as was done from the IR cell.
Monitoring of the surface species by hydrolysis after alkane
metathesis
The catalyst was introduced into a batch reactor as described
above and the metathesis reaction run for a given time. After
stopping, the gas phase of the reactor was evacuated and a
vapor of water (18 Torr) was introduced. Alkanes were ana-
lyzed as above and hydrogen on an Intersmat IGC 120MB gas
chromatograph equipped with a katharometer detector and a
filled molecular sieves column (3 m × 3.2 mm).
16 V. Dufaud, G. P. Niccolai, J. Thivolle-Cazat and J.-M. Basset,
J. Am. Chem. Soc., 1995, 117, 4288–4294.
17 L. Lefort, M. Chabanas, O. Maury, D. Meunier, C. Copéret,
J. Thivolle-Cazat and J.-M. Basset, J. Organomet. Chem.,
2000, 593–594, 96–100.
Metathesis of alkanes in a continuous flow reactor
[(SiO)2Ta–H]/MCM-41, 2, (250 mg; 11.7 wt% Ta) was
charged within a glove-box into a stainless steel 0.5 inch
diameter continuous flow reactor fitted with
a four-
channels isolating valve. After connection to the rack, all
the tubing was purged under a flow (3 ml min−1) of the
desired alkane. The four-channel valve was then switched
on and the alkane was sent through the catalytic bed with
a flow rate (3 ml min−1) maintained constant using a mass
flow controller, then the oven was heated to 150 °C within
50 min. The gas products, alkanes and hydrogen were
analyzed on line with a Varian micro-GC CP-4900 using cap-
illary columns (10 m PPU; 6 m 5CB; 10 m Al2) and
katharometer detectors.
18 E. Le Roux, M. Chabanas, A. Baudouin, A. de Mallmann,
C. Coperet, E. A. Quadrelli, J. Thivolle-Cazat, J.-M. Basset,
W. Lukens, A. Lesage, L. Emsley and G. J. Sunley, J. Am.
Chem. Soc., 2004, 126, 13391–13399.
19 S. Soignier, M. Taoufik, E. Le Roux, G. Saggio,
C. Dablemont, A. Baudouin, F. Lefebvre, A. De Mallmann,
J.
Thivolle-Cazat,
J.-M.
Basset,
G.
Sunley
and
B. M. Maunders, Organometallics, 2006, 25, 1569–1577.
20 O. Maury, G. Saggio, A. Theolier, M. Taoufik, V. Vidal,
J. Thivolle-Cazat and J.-M. Basset, C. R. Acad. Sci., 2000, 3,
583–587.
21 C. Thieuleux, E. A. Quadrelli, J.-M. Basset, J. Doebler and
J. Sauer, Chem. Commun., 2004, 1729–1731.
22 M. Taoufik, A. de Mallmann, E. Prouzet, G. Saggio,
J. Thivolle-Cazat and J.-M. Basset, Organometallics, 2001, 20,
5518–5521.
Acknowledgements
The authors wish to kindly acknowledge ESCPE-Lyon, CNRS,
UCB-Lyon and particularly the BP Chemicals Company which
supported this work.
23 R. Anwander and R. Roesky, J. Chem. Soc., Dalton Trans.,
1997, 137–138.
References
1 Activation and Functionalization of Alkanes, ed. C. L. Hill,
J. Wiley & Sons, Inc., New York, 1989.
2 R. H. Crabtree, J. Organomet. Chem., 2004, 689, 4083–4091.
3 A. S. Goldman, A. H. Roy, Z. Huang, R. Ahuja, W. Schinski
and M. Brookhart, Science, 2006, 312, 257–261.
24 R. M. Gauvin, L. Delevoye, R. A. Hassan, J. Keldenich and
A. Mortreux, Inorg. Chem., 2007, 46, 1062–1070.
25 F. Blanc, J. Thivolle-Cazat, J.-M. Basset, C. Coperet,
A. S. Hock, Z. J. Tonzetich and R. R. Schrock, J. Am. Chem.
Soc., 2007, 129, 1044–1045.
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