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

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)3468-3475
Number of pages8
JournalOrganometallics
Volume24
Issue number14
DOIs
Publication statusPublished - Jul 4 2005
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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