Reactions of a hydrido(hydrosilylene)tungsten complex with oxiranes

Hisako Hashimoto, Mitsuyoshi Ochiai, Hiromi Tobita

Research output: Contribution to journalArticlepeer-review

21 Citations (Scopus)

Abstract

Reactivity of a hydrido(hydrosilylene)tungsten complex, Cp*(CO)2(H)W{double bond, long}Si(H)[C(SiMe3)3] (1), toward oxiranes was investigated. Treatment of 1 with racemic mono-substituted oxiranes with a substituent R (R = Ph, vinyl, tBu, or nBu) at room temperature produced dihydrido(vinyloxysilyl)tungsten complexes, (E)- and/or (Z)-Cp*(CO)2(H)2W{Si(H)(OCH{double bond, long}CHR)[C(SiMe3)3]} [(E/Z)-2: R = Ph, (E)-3: R = vinyl, (E)-4: R = tBu, (E/Z)-5: R = nBu] in high yields via regioselective ring-opening of oxiranes. When the substituent R on oxirane was relatively large, (E)-isomers (2, 3, and 4) were obtained predominantly (87-97%), while the substituent was a relatively small nBu group, an approximately 1:1 mixture of (E)- and (Z)-isomers [(E/Z)-5] was obtained. Reaction of 1 with 2,2-dimethyloxirane afforded the corresponding complex, Cp*(CO)2(H)2W{Si(H)(OCH{double bond, long}CMe2)[C(SiMe3)3]} (6), quantitatively. A reaction mechanism is also discussed.

Original languageEnglish
Pages (from-to)36-43
Number of pages8
JournalJournal of Organometallic Chemistry
Volume692
Issue number1-3
DOIs
Publication statusPublished - 2007 Jan 1

Keywords

  • (E/Z)-isomers
  • Hydrido complex
  • Oxirane
  • Ring-opening reaction
  • Silyl complex
  • Silylene complex
  • Vinyl group

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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