A bowl-shaped phosphine as a ligand in rhodium-catalyzed hydrosilylation: Rate enhancement by a mono(phosphine) rhodium species

Osamu Niyomura, Tetsuo Iwasawa, Naoki Sawada, Makoto Tokunaga, Yasushi Obora, Yasushi Tsuji

研究成果: ジャーナルへの寄稿学術誌査読

77 被引用数 (Scopus)

抄録

Bowl-shaped phosphine (BSP) ligands markedly accelerated the rhodium-catalyzed hydrosilylation of ketones and ketimines as compared with the effect of conventional phosphine ligands such as PPh 3 and P(t-Bu) 3. 31P NMR study of a mixture of [RhCl(C 2H 4) 2] 2 and phosphines at various P/Rh ratios revealed that coordination of BSP to the rhodium metal was successfully regulated, and the resultant rhodium complex bearing only one phosphine ligand (a mono(phosphine) rhodium species) was responsible for the acceleration. Structural comparison between BSP and the conventional phosphines was carried out using HF/6-31G(d)-CONFLEX/MM3-optimized structures. The mono(phosphine) rhodium complex having 1,5-cyclooctadiene as a ligand was isolated, and its X-ray molecular structure was determined.

本文言語英語
ページ(範囲)3468-3475
ページ数8
ジャーナルOrganometallics
24
14
DOI
出版ステータス出版済み - 7月 4 2005
外部発表はい

!!!All Science Journal Classification (ASJC) codes

  • 物理化学および理論化学
  • 有機化学
  • 無機化学

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