Stoichiometric hydrosilylation of nitriles with hydrido(hydrosilylene) tungsten complexes: Formation of W-Si-N three-membered ring complexes and their unique thermal behaviors

Takahito Watanabe, Hisako Hashimoto, Hiromi Tobita

Research output: Contribution to journalArticlepeer-review

63 Citations (Scopus)

Abstract

Reactions of hydrido(hydrosilylene)tungsten complexes, Cp′(CO) 2 (H)W=Si(H)[C(SiMe 3 ) 3 ], with nitriles (MeCN, t BuCN) at 60 °C gave hydrosilylation products, Cp′(CO) 2 W[κ 2 (N,Si)-Si(H)(N=CHR′){C(SiMe 3 ) 3 }] (R′ = Me, t Bu), with a novel W-Si-N three-membered ring structure. The product of the hydrosilylation of t BuCN underwent reversible rearrangement at 70 °C to a silylene complex, Cp′(CO) 2 (H)W=Si(N=CH t Bu)[C(SiMe 3 ) 3 ], which was a major component in equilibrium. A reaction mechanism for the hydrosilylation involving coordination of nitriles to the silylene ligand and subsequent migration of the hydrido ligand to the nitrile carbon was proposed.

Original languageEnglish
Pages (from-to)2176-2177
Number of pages2
JournalJournal of the American Chemical Society
Volume128
Issue number7
DOIs
Publication statusPublished - 2006 Feb 22

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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