Hydrido(hydrosilylene)tungsten complexes: Dynamic behavior and reactivity toward acetone

Takahito Watanabe, Hisako Hashimoto, Hiromi Tobita

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)

Abstract

Reaction of a labile tungsten nitrile complex, [(Cp*)W(CO) 2(NCMe)Me] (Cp*=η 5-C 5Me 5), with H 3SiC(SiMe 3) 3 gave the hydrido(hydrosilylene) complex [(Cp*)(CO) 2(H)W=Si(H) {C(SiMe 3) 3}] (1a). The hydrido(silylene) complex [(η 5-C 5Me 4Et)(CO) 2(H)W= SiMes 2] (2) (Mes=2,4,6-Me-C 6H 2) was synthesized by a similar reaction with H 2SiMes 2. There is a strong interligand interaction between the hydrido and silylene ligands of these complexes; this was confirmed by a neutron diffraction study of [D 2]1b, that is, the deuterido and η 5-C 5Me 4Et derivative of 1a. The exchange between the W-H and the Si-D groups was observed in the deuterido complex [D]1a. This H/D exchange proceeded slowly at room temperature, but very rapidly under UV irradiation. Variable-temperature NMR spectroscopy measurements show the dynamic behavior of carbonyl ligands in 1a. Complex 1a reacted with acetone at room temperature to give mainly a hydrosilylation product, [(Cp*)(CO) 2(H)W=Si(OiPr) {C(SiMe 3) 3}] (3a), along with a siloxy complex, [(Cp*)(CO) 2WO(Si(H)iPr{C(SiMe 3) 3})] (4a). At low temperature, a different reaction, namely, α-H abstraction, proceeded to give an equilibrium mixture of 1a and a dihydrido(silyl) complex, [(Cp*)(CO) 2(H) 2W(Si(H){OC(=CH 2)Me} {C(SiMe 3) 3})] (5).

Original languageEnglish
Pages (from-to)1408-1416
Number of pages9
JournalChemistry - An Asian Journal
Volume7
Issue number6
DOIs
Publication statusPublished - 2012 Jun

Keywords

  • Si ligand
  • dynamic behavior
  • hydrides
  • ligand effects
  • tungsten

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry

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