Synthesis, structure, and reactivity of hydridobis(silylene)ruthenium(IV)- xantsil complexes (xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)) - A stabilized form of key intermediates in the catalytic oligomerization- deoligomerization of hydrosilanes

Masaaki Okazaki, Jim Josephus Gabrillo Minglana, Nobukazu Yamahira, Hiromi Tobita, Hiroshi Ogino

Research output: Contribution to journalArticlepeer-review

19 Citations (Scopus)

Abstract

Ru {K2(Si,Si)-xantsil}(CO)(η6-C6H 5CH3) (1) was found to be a catalyst for oligomerization-deoligomerization of HSiMe2SiMe3 to give H(SiMe2)nMe (n = 1-8 at 90°C for 2 days). Treatment of 1 with HSiMe2SiMe2OR (R = Me, f-Bu) led to quantitative formation of Ru{κ3(O,Si,Si)-xantsil}(CO)(H) {(SiMe2⋯O(R)⋯SiMe2)} (R = Me (2a), t-Bu (2b)), which also worked as a catalyst for oligomerization-deoligomerization of HSiMe2SiMe3. Based on these experimental results, a mechanism involving silyl(silylene) intermediates was proposed for the oligomerization-deoligomerization of HSiMe2SiMe3. Complex 2a reacted with MeOH in toluene-d8 to give Ru{κ 2(Si,Si)-xantsil}(CO)(η6-toluene-d8) and Me2Si(OMe)2 with evolution of H2. Under a CO atmosphere, 2a was smoothly converted to its CO adduct Ru{κ 2(Si-Si)-xantsil}(CO)2(H){(SiMe2⋯O(Me) ⋯SiMe2)} (3).

Original languageEnglish
Pages (from-to)1350-1358
Number of pages9
JournalCanadian Journal of Chemistry
Volume81
Issue number11
DOIs
Publication statusPublished - 2003 Nov 1

Keywords

  • Dehydrogenative coupling
  • Oligomerization
  • Polysilane
  • Ruthenium
  • Silylene complex

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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