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On the Use of Ruthenium Dioxide in 1-n-Butyl-3-Methylimidazolium Ionic Liquids as Catalyst Precursor for Hydrogenation Reactions

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Abstract

The H2 reduction of RuO2 hydrate “dissolved” in 1-n-butyl-3-methylimidazolium ionic liquids with different counterions, hexafluorophosphate (BMI ⋅ PF6), tetrafluoroborate (BMI ⋅ BF4) and trifluoromethane sulfonate (BMI ⋅ SO3CF3), is a simple and reproducible method for the preparation of ruthenium nanoparticles of 2.0–2.5 nm diameter size and with a narrow size distribution. The Ru nanoparticles were characterized by TEM and XRD. The isolated Ru nanoparticles are reoxidized in air, whereas they are less prone to oxidation when imbibed in the ionic liquids. These nanoparticles are active catalysts for the solventless or liquid–liquid biphasic hydrogenation of olefins under mild reaction conditions (4 atm, 75°C). The catalytic system composed of nanoparticles dispersed in BMI ⋅ PF6 ionic liquid is very stable and can be reused several times without any significant loss in the catalytic activity. Total turnover numbers greater than 110 000 (based on total Ru) or 320 000 (corrected for exposed Ru atoms) were attained within 80 h for the hydrogenation of 1-hexene.

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References

  1. H. Over, Y.D. Kim, A.P. Seitsonen, S. Wendt, E. Lundgren, M. Schmid, P. Varga, A. Morgante and G. Ertl, Science 287 (2000) 1474; (b) L. Zang and H. Kisch, Angew. Chem., Int. Ed. 39 (2000) 3921; (c) A. Böttcher, M. Rogozia, H. Niehus, H. Over and G. Ertl, J. Phys. Chem., B 103 (1999) 6267.

    Google Scholar 

  2. A. Mills, Chem. Soc. Rev. 18 (1989) 285; (b) H. Harriman, Platinum Met. Rev. 27 (1983) 102; (c) W.D. An, J.K. Hong, P.N. Pintauro, K. Warner and W. Neff, J. Am. Oil Chem. Soc. 75 (1998) 917.

    Google Scholar 

  3. H. Madhavaram, H. Idriss, S. Wendt, Y.D. Kim, M. Knapp, H. Over, J. Aßmann, E. Löffler and M. Muhler, J. Catal. 202 (2001) 296.

    Google Scholar 

  4. K. Kaneda, S. Haruna, T. Imanaka and K. Kawamoto, J. Chem. Soc., Chem. Commun. (1990) 1467.

  5. B.-Z. Zhan, M.A. White, T.-K. Sham, J.A. Pincock, R.J. Doucet, K.V.R. Rao, K.N. Robertson and T.S. Cameron, J. Am. Chem. Soc. (2003) in press.

  6. See for example: R. Kikuchi, F. Mizukami, S. Niwa, M. Toba, H. Ushijima and K. Itou, Appl. Chem., A: Gen. 165 (1997) 309 and references therein.

    Google Scholar 

  7. O. Vidoni, K. Philippot, C. Amiens, B. Chaudret, O. Balmes, J.O. Malm, J.O. Bovin, F. Senocq and M.J. Casanove, Angew. Chem., Int. Ed. 38 (1999) 3736; (b) K. Pelzer, O. Vidoni, K. Philippot, B. Chaudret and V. Colliere, Adv. Funct. Mater. 13 (2003) 118; (c) W. Yu, M. Liu, H. Liu, X. Ma and Z. Liu, J. Colloid Interface Sci. 208 (1998) 439; (d) M. Liu, W. Yu and H. Liu, J. Mol. Catal., A: Chem. 138 (1999) 295; (e) A. Miyazaki, K. Takeschita, K. Aika and Y. Nakano, Chem. Lett. (1998) 361; (f) Y. Wang, J. Ren, K. Deng, L. Gui and Y. Tang, Chem. Mater. 12 (2000) 1622; (g) H. Hirai, Y. Nakao and T. Toshima, J. Macromol. Sci. Chem., A 13 (1979) 727; (h) L.N. Lewis and L. Lewis, Chem. Mater. 1 (1989) 106; (i) A. Duteil, R. Quéau, B. Chaudret, R. Mazel, C. Roucau and J. S. Bradley, Chem. Mater. 5 (1993) 341; (j) H. Bönnemann, W. Brijoux, R. Brinkmann, R. Fretzen, T. Jounsen, T. Köppler, P. Neitteler and J. Richter, J. Mol. Catal. 86 (1994) 129; (l) J.-M. Planeix, N. Coustel, B. Coq, V. Brotons, P.S. Kumbhar, R. Dutartre, P. Geneste, P. Bernier and P.M. Ajayan, J. Am. Chem. Soc. 116 (1994) 7935; (m) W. Tu and H. Liu, Mater. Chem. 10 (2000) 2207; (n) S. Gao, J. Zhang, Y.-F. Zhu and C.-M. Che, New J. Chem. 24 (2000) 739; (o) G. Viau, P. Toneguzzo, A. Pierrard, O. Acher, F. Fiévet-Vincent and F. Fiévet, Scr. Mater. 44 (2001) 2263; (p) A. Spitaleri, P. Pertici, N. Scalera, G. Vitulli, M. Hoang, T.W. Turney and M. Gleria, Inorg. Chim. Acta (2003) in press.

    Google Scholar 

  8. J. Dupont, G.S. Fonseca, A.P. Umpierre, P.F.P. Fichtner and S.R. Texeira, J. Am. Chem. Soc. 124 (2002) 4228; (b) G.S. Fonseca, A.P. Umpierre, J. Dupont, P.F.P Fichtner and S.R. Texeira, Chem. Eur. J. 14 (2003) 3263; (c) C.W. Scheeren, G. Machado, J. Dupont, P.F.P. Fichtner, S.R. Texeira, Inorg. Chem. 42 (2003) 4738.

    Google Scholar 

  9. J. Dupont, P.A.Z. Suarez, R.F. de Souza, R.A. Burrow and J.P. Kintzinger, Chem. Eur. J. 6 (2000) 2377; (b) J.D. Wadhawan, U. Schroder, A. Neudeck, S.J. Wilkins, R.G. Compton, F. Marken, C.S. Consorti, R.F. de Souza and J. Dupont, J. Eletroanal. Chem. 493 (2000) 75; (c) U. Schroder, J.D. Wadhawan, R.G. Compton, F. Marken, P.A.Z. Suarez, C.S. Consorti, R.F. de Souza and J. Dupont, New J. Chem. 24 (2000) 1009.

    Google Scholar 

  10. For a recent review about ionic liquids see: J. Dupont, R.F. de Souza and P.A.Z. Suarez, Chem. Rev. 102 (2002) 3667.

    Google Scholar 

  11. For hydrogenation reactions promoted by transition-metal complexes in imidazolium ionic liquids see: (a) P.G. Jessop, R.R. Stanley, R.A. Brown, C.A. Eckert, C.L. Liotta, T.T. Ngo and P. Pollet, Green. Chem. 5 (2003) 123; (b) J. Navarro, M. Sagi, E. Sola, F.J. Lahoz, I.T. Dobrinovitch, A. Katho, F. Joo and L.A. Oro, Adv. Synth. Catal. 345 (2003) 280; (c) C.S. Consorti, A.P. Umpierre, R.F. de Souza, J. Dupont and P.A.Z. Suarez, J. Braz. Chem. Soc. 14(2003) 401; (d) C.J. Boxwell, P.J. Dyson, D.J. Ellis and T. Welton, J. Am. Chem. Soc. 124 (2002) 9334; (e) P.J. Dyson, Appl. Organomet. Chem. 16 (2002) 495; (f) C.P. Mehnert, E.J. Mozeleski and R.A. Cook, Chem. Commun. 3010 (2002); (g) R.A. Brown, P. Pollet, E. McKoon, C.A. Eckert, C.L. Liotta and P.G. Jessop, J. Am. Chem. Soc. 123 (2001) 1254; (h) S. Guernik, A. Wolfson, M. Herskowitz, N. Greenspoon and S. Geresh, Chem. Commun. (2001) 2314; (i) A. Berger, R.F. de Souza, M.R. Delgado and J. Dupont, Tetrahedron: Asymmetry 12 (2001) 1825; (j) J. Dupont, P.A.Z. Suarez, A.P. Umpierre and R.F. de Souza, Catal. Lett. 73 (2001) 211; (l) P.J. Dyson, D.J. Ellis and T. Welton, Can. J. Chem. 79 (2001) 705; (m) S. Steines, P. Wasserscheid and B.J. Driessen-Holscher, Prakt. Chem. 342 (2000) 348; (n) A.L. Monteiro, F.K. Zinn, R.F. de Souza and J. Dupont, Tetrahedron: Asymmetry 8 (1997) 177; (o) P.A.Z. Suarez, J.E.L. Dullius, S. Einloft, R.F. de Souza and J. Dupont, Inorg. Chim. Acta 255 (1997) 207; (p) Y. Chauvin, L. Mussmann and H. Olivier, Angew. Chem., Int. Ed. Engl. 34 (1996) 2698.

  12. P.A.Z. Suarez, J.E.L. Dullius, S. Einloft, R.F. de Souza and J. Dupont, Polyhedron 15 (1996) 1217; (b) J. Dupont, P.A.Z. Suarez, C.S. Consorti and R.F. de Souza, Org. Synth. 79 (2002) 236.

    Google Scholar 

  13. B.K. Sweeny and D.G. Peters, Electrochem. Commun. 3 (2001) 712.

    Google Scholar 

  14. For a detailed discussion of CS2 and Hg(0) poisoning tests see: (a) K.S. Weddle, J.D. Aiken and R.G. Finke, J. Am. Chem. Soc. 120 (1998) 5653; (b) B.J. Hornstein, J.D. Aiken and R.G. Finke, Inorg. Chem. 41 (2002) 1625.

  15. For the physical-chemical properties of imidazolium ionic liquids see: (a) P.A.Z. Suarez, S. Einloft, J.E.L. Dullius, R.F. de Souza and J. Dupont, J. Chim. Phys. Phys.-Chim. Biol. 95 (1998) 1626; (b) J.E.L. Dullius, P.A.Z. Suarez, S. Einloft, R.F. de Souza, J. Dupont, J. Fischer and A. De Cian, Organometallics 17 (1998) 815.

  16. R.G. Finke, in Transition-Metal Nanoclusters, D.L. Feldheim and C.A. Foss Jr. (eds), Chapter. 2 (Marcel Dekker, New York, 2002) pp. 17-54.

    Google Scholar 

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Rossi, L.M., Machado, G., Fichtner, P.F.P. et al. On the Use of Ruthenium Dioxide in 1-n-Butyl-3-Methylimidazolium Ionic Liquids as Catalyst Precursor for Hydrogenation Reactions. Catalysis Letters 92, 149–155 (2004). https://doi.org/10.1023/B:CATL.0000014337.40179.4a

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  • DOI: https://doi.org/10.1023/B:CATL.0000014337.40179.4a

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