Then, sodium borohydride (1.37 mg, 3.6 × 10− mol) in 2 mL
of water was added all at once under vigorous stirring at room
temperature. The solution was stirred for 24 h at room temperature
before use.
2
3 (a) M. Tamura and H. Fujihara, J. Am. Chem. Soc., 2003, 125, 15742;
(
b) M. T. Reetz, R. Breinbauer and K. Wanninger, Tetrahedron Lett.,
1
996, 37, 4499; (c) M. T. Reetz and E. Westermann, Angew. Chem., Int.
Ed., 2000, 39, 165; (d) M. Moreno-Ma n˜ as, R. Pleixats and S. Villarroya,
Organometallics, 2001, 20, 4524; (e) C. Rocaboy and J. A. Gladysz, Org.
Lett., 2002, 4, 1993; (f) K. H. Park and Y. K. Chung, Synlett, 2005, 4,
5
45.
Synthesis of surfactant stabilized aqueous ruthenium(0) suspension
4
(a) A. Roucoux, in Surface and Interfacial Organometallic Chemistry
and Catalysis in Topics in Organometallic Chemistry, ed. C. Cop e´ ret,
B. Chaudret, Springer-Verlag, 2005, vol. 16, p. 261; (b) A. Roucoux,
K. Philippot, Hydrogenation with noble metal nanoparticles in The
Handbook of Homogeneous Hydrogenation, ed. J. G. de Vries, Wiley-
VCH, Weinheim, 2006.
An aqueous solution of surfactant HEA16Cl (544 mg, 1.7 ×
−
3
−1
10
mol L in 40 mL H O) was added to a flask containing
2
−
4
1
6 mg of sodium borohydride (4.2 × 10 mol). Then this solution
was quickly added under vigorous stirring to an aqueous solution
5
6
7
(a) P. J. Dyson, Dalton Trans., 2003, 2964; (b) J. A. Widegren and
R. G. Finke, J. Mol. Catal. A: Chem., 2003, 198, 317; (c) C. M.
Hagen, L. Vieille-Petit, G. Laurenczy, G. S u¨ ss-Fink and R. G. Finke,
Organometallics, 2005, 24, 1819.
(a) Industrial Organic Chemistry, ed. K. Weissermel and H. J. Arpe,
Wiley-VCH, New York, 2nd edn, 1993, p. 343; (b) S. Matar, L. F.
Hatch, Chemistry and Petrochemical Processes, 2nd edn, Butterworth-
Heinemann, Boston, 2001, 281.
−
4
(
10 mL) of the RuCl
3
salt (50 mg, 1.7 × 10 mol) to obtain
an aqueous Ru(0) colloidal suspension (50 mL). The reduction
occurs instantaneously and is characterized by a color change
from yellow–brown to black. The solution was stirred for 24 h at
room temperature before use.
H. Nagahara, M. Ono, M. Konishi and Y. Fukuoka, Appl. Surf. Sci.,
General procedure for hydrogenation
1
997, 121/122, 448.
8
9
B. H. Cooper and B. B. L. Donnis, Appl. Catal., A, 1996, 137, 203.
Aqueous-Phase Organometallic Catalysis, ed. B. Cornils, Wiley-VCH,
Weinheim, 1998.
1
0 mL of the previously prepared aqueous suspension of Ru(0)
were introduced in to a 50 mL flask. The appropriate substrate
−
3
(
1.44 × 10 mol) of substrate was added. The reaction mixture
10 (a) J. Liu, R. Xu and A. E. Kaifer, Langmuir, 1998, 14, 7337; (b) J.
Liu, S. Mendoza, E. Roman, M. J. Lynn, R. Xu and A. E. Kaifer,
J. Am. Chem. Soc., 1999, 121, 4304; (c) J. Liu, W. Ong, E. Roman, M. J.
Lynn and A. E. Kaifer, Langmuir, 2000, 16, 3000; (d) J. Alvarez, J. Liu,
E. Roman and A. E. Kaifer, Chem. Commun., 2000, 1151; (e) J. Liu,
J. Alvarez, W. Ong, E. Roman and A.E. Kaifer, Langmuir, 2001, 17,
was stirred vigorously, at room temperature under 1 bar of H
2
until the reaction was finished. The reaction was monitored by the
volume of hydrogen consumed and gas chromatographic analysis.
6
762; (f) J. Liu, J. Alvarez, W. Ong, E. Roman and A. E. Kaifer, J. Am.
TEM analysis
Chem. Soc., 2001, 123, 1148; (g) L. Strimbu, J. Liu and A. E. Kaifer,
Langmuir, 2003, 19, 483.
The transmission electronic microscopic studies were conducted
using a PHILIPS CM 12 transmission electron microscope at
1
1
1 A. Nowicki, Y. Zhang, B. L e´ ger, J. P. Rolland, H. Bricout, E. Monflier
and A. Roucoux, Chem. Commun., 2006, 296.
00 KeV (UMR 6026-University of Rennes I). Samples were
12 For substrate selective reactions promoted by modified cyclodextrins,
see: (a) T. Lacroix, H. Bricout, S. Tilloy and E. Monflier, Eur. J. Org.
Chem., 1999, 3127; (b) H. Bricout, L. Caron and E. Monflier, Catal.
Today, 2001, 66, 355; (c) J. Cabou, H. Bricout, F. Hapiot and E.
Monflier, Catal. Commun., 2004, 5, 265; (d) C. Torque, H. Bricout,
F. Hapiot and E. Monflier, Tetrahedron, 2004, 60, 6487; (e) C. Torque,
B. Sueur, J. Cabou, H. Bricout, F. Hapiot and E. Monflier, Tetrahedron,
prepared by a dropwise addition of the CD-stabilized ruthenium
colloids in water onto a copper sample mesh covered with carbon.
The colloidal dispersion was partially removed after 1 min using
cellulose before transferring to the microscope. The picture is
obtained at × 200.000 on Kodak SO-163 film. Measurement of
2
005, 61, 4811.
2
40 particles was made with the program SCION Image (NIH)
1
1
1
3 (a) D. Chouchi, D. Gourgouillon, M. Courel, J. Vital and M. Nunes da
Ponte, Ind. Eng. Chem. Res., 2001, 40, 2551; (b) T. C. Chou, J. Y. Lin,
C. H. Lian and J. S. Do, Ind. Eng. Chem. Res., 1990, 29, 180.
and was analyzed with an excel program providing histograms of
the nanoparticle size distribution.
4 (a) E. Monflier, S. Tilloy, G. Fremy, Y. Barbaux and A. Mortreux,
Tetrahedron Lett., 1995, 36, 387; (b) E. Monflier, S. Tilloy, G. Fremy, Y.
Castanet and A. Mortreux, Tetrahedron Lett., 1995, 36, 9481.
5 (a) J. Schulz, A. Roucoux and H. Patin, Chem. Commun., 1999, 535;
(b) J. Schulz, A. Roucoux and H. Patin, Chem.–Eur. J., 2000, 6, 618;
(c) A. Roucoux, J. Schulz and H. Patin, Adv. Synth. Catal., 2002, 345,
222; (d) V. M e´ vellec, A. Roucoux, E. Ramirez, K. Philipot and B.
Chaudret, Adv. Synth. Catal., 2004, 346, 72.
Notes and references
1
(a) Nanoparticles. From theory to application, ed. G. Schmid, Wiley-
VCH, Weinheim, 2004; (b) D. L. Feldheim, C. A. Foss, Jr., in
Metal Nanoparticles: Synthesis, Characterization and Applications, ed.
Marcel Dekker, New York, 2002; (c) K. J. Klabunde, G. Cardenas-
Trivano, in Active Metals Preparation, Characterization, Applications,
ed. A. F u¨ rstner, Wiley-VCH, Weinheim, 1996, p 237.
16 A. Nowicki, V. Le Boulaire and A. Roucoux, Adv. Synth. Catal., 2007,
DOI: 10.1002/adsc.200700208.
2
(a) H. B o¨ nneman and R. M. Richards, Eur. J. Inorg. Chem., 2001, 2455;
17 Y. Liu, K. B. Male, P. Bouvrette and J. H. T. Luong, Chem. Mater.,
(
(
b) A. Roucoux, J. Schulz and H. Patin, Chem. Rev., 2002, 102, 3757;
c) D. Astruc, F. Lu and J. R. Aranzes, Angew. Chem., Int. Ed., 2005,
4, 7852; (d) A. Roucoux, A. Nowicki, K. Philippot, in Nanoparticles
2003, 15, 4172.
18 Y. Huang, D. Li and J. Li, Chem. Phys. Lett., 2004, 389, 14.
19 Y. Kenechi, M. Atsushi, T. Yukio, S. Mitsukatsu, Y. Yoshiaki, I.
Tomoyuki, JP pat. 8333406, 1996.
4
and Catalysis, ed D. Astruc, Wiley-VCH, Weinheim, 2007, p. 351.
This journal is © The Royal Society of Chemistry 2007
Dalton Trans., 2007, 5714–5719 | 5719