The pressure was kept constant during the monitoring by an
external hydrogen reservoir. To monitor the hydrogenation of
acetophenone, the same conditions and ruthenium/substrate
ratios were applied.
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5
2
3
4
Hg poisoning test
Hg poisoning tests were carried out using the same
standard hydrogenation conditions. Bis(methylallyl)(1,5-cyclo-
octadiene)ruthenium(II) (5.1 mg; 0.016 mmol) was dispersed in
5 (a) J. Dupont and J. D. Scholten, Chem. Soc. Rev., 2010, 39, 1780;
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Weinheim; (c) D. Astruc, F. Lu and J. R. Aranzaes, Angew. Chem.,
[
6
C
12MIM][BTA] (62.0 mg; 0.117 mmol). After stirring for 2 h at
◦
0 C and 60 bar H
2
pressure 2 (217.8 mg, 1.60 mmol) was added.
2
005, 117, 8062; D. Astruc, F. Lu and J. R. Aranzaes, Angew. Chem.,
The reactor was pressurized to 120 bar hydrogen and heated to
Int. Ed., 2005, 44, 7852.
◦
1
20 C. After 1 h reaction time, the reaction was cooled down
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8995.
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to ambient temperature and carefully vented. A small sample
was collected to be analyzed by GC. Elemental Hg (1.355 g, 422
equiv.) was added to the reaction mixture. After stirring for 10 h,
◦
the reaction mixture was heated to 120 C and pressurized to
7
1
20 bar with hydrogen for 1 h. Afterwards the reactor was cooled
down, depressurized and a sample was taken for GC analysis.
The Hg poisoning reaction with RuHCl(PPh
carried out under the same conditions.
3
)
3
as catalyst was
8 J. D. Aiken and R. G. Finke, J. Mol. Catal. A: Chem., 1999, 145,
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0 M. Antonietti, D. B. Kuang, B. Smarsly and Y. Zhou, Angew. Chem.,
2
Recycling
1
For recycling, the products were extracted with scCO from the
2
2
004, 116, 5096; M. Antonietti, D. B. Kuang, B. Smarsly and Y.
reaction mixture after the reaction. The extraction was carried
Zhou, Angew. Chem., Int. Ed., 2004, 43, 4988.
◦
1
1
1 L. S. Ott, M. L. Cline, M. Deetlefs, K. R. Seddon and R. G. Finke,
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1525.
out at 40 C and 150 bar CO
2
pressure for 3 h with an average
-
1
flow rate of 287.5 mL min under continuous conditions. The
extract was collected in a cooling trap kept at -45 C in a 2-
◦
propanol/dry ice bath.
1
Acknowledgements
This work was supported by the Deutsche Bundesstiftung
Umwelt (DBU) and in part by the Cluster of Excellence
1
1
1
5 J. A. Widegren and R. G. Finke, J. Mol. Catal. A: Chem., 2003, 198,
“
Tailor-Made Fuels from Biomass” (TMFB), which is funded
3
17.
by the Excellence Initiative of the German federal and state
governments to promote science and research at German
universities. TEM measurements by B. Spliethoff (MPI f u¨ r
Kohleforschung, M u¨ lheim/Ruhr) are gratefully acknowledged.
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Dupont, J. Am. Chem. Soc., 2005, 127, 3298; (b) J. G. de Vries,
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Organomet. Chem., 2008, 22, 288.
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4
07; (b) J. S. Wilkes, J. A. Levisky, R. A. Wilson and C. L. Hussey,
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Green Chem., 2010, 12, 1634–1639 | 1639