Catalytic hydrogenation of CO and CN bonds via heterolysis of H2 mediated by metal-sulfur bonds of rhodium and iridium thiolate complexes |
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Authors: | Mayumi Sakamoto Gerald Kehr Kazuyuki Tatsumi |
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Institution: | a Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan b Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, D-48149 Münster, Germany |
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Abstract: | Coordinatively unsaturated rhodium and iridium complexes having a bulky thiolate, Cp∗M(PMe3)(SDmp)](BArF4) (1a: M = Rh; 1b: M = Ir; Dmp = 2,6-(mesityl)2C6H3, ArF = 3,5-(CF3)2C6H3), catalyzed the hydrogenation of benzaldehyde, N-benzylideneaniline, and cyclohexanone, under 1 atm of H2 at low temperatures. In these catalytic reactions, the M-H/S-H complexes Cp∗M(PMe3)(H)(HSDmp)](BArF4) (2a: M = Rh; 2b: M = Ir) generated via H2 heterolysis by 1a or 1b were suggested to transfer both M-H hydride and S-H proton to substrates. The catalytic reactions were terminated by the dissociation of H-SDmp from the metal centers of 2a and 2b that occurs at ambient temperature under H2 atmosphere. |
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Keywords: | Rhodium Iridium Thiolate H2 activation Hydrogenation |
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