μ3‐η2:η2:η2‐Coordination of Primary Silane on a Triruthenium Plane |
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| Authors: | Masahiro Nagaoka Hiroyuki Tsuruda Dr Masa‐aki Amako Prof?Dr Hiroharu Suzuki Prof?Dr Toshiro Takao |
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| Institution: | 1. Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, O‐okayama, Meguro‐ku, Tokyo 152‐8552 (Japan);2. JST, ACT‐C, 4‐1‐8 Honcho, Kawaguchi, Saitama, 332‐0012 (Japan) |
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| Abstract: | A μ3‐η2:η2:η2‐silane complex, (Cp*Ru)3(μ3‐η2:η2:η2‐H3SitBu)(μ‐H)3] ( 2 a ; Cp*=η5‐C5Me5), was synthesized from the reaction of {Cp*Ru(μ‐H)}3(μ3‐H)2] ( 1 ) with tBuSiH3. Complex 2 a is the first example of a silane ligand adopting a μ3‐η2:η2:η2 coordination mode. This unprecedented coordination mode was established by NMR and IR spectroscopy as well as X‐ray diffraction analysis and supported by a density functional study. Variable‐temperature NMR analysis implied that 2 a equilibrates with a tautomeric μ3‐silyl complex ( 3 a ). Although 3 a was not isolated, the corresponding μ3‐silyl complex, (Cp*Ru)3(μ3‐η2:η2‐H2SiPh)(H)(μ‐H)3] ( 3 b ), was obtained from the reaction of 1 with PhSiH3. Treatment of 2 a with PhSiH3 resulted in a silane exchange reaction, leading to the formation of 3 b accompanied by the elimination of tBuSiH3. This result indicates that the μ3‐silane complex can be regarded as an “arrested” intermediate for the oxidative addition/reductive elimination of a primary silane to a trinuclear site. |
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| Keywords: | agostic interactions cluster compounds ruthenium Si ligands structure elucidation |
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