TY - JOUR
T1 - 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
AU - Okazaki, Masaaki
AU - Minglana, Jim Josephus Gabrillo
AU - Yamahira, Nobukazu
AU - Tobita, Hiromi
AU - Ogino, Hiroshi
PY - 2003/11/1
Y1 - 2003/11/1
N2 - 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).
AB - 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).
KW - Dehydrogenative coupling
KW - Oligomerization
KW - Polysilane
KW - Ruthenium
KW - Silylene complex
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U2 - 10.1139/v03-151
DO - 10.1139/v03-151
M3 - Article
AN - SCOPUS:1642580806
VL - 81
SP - 1350
EP - 1358
JO - Canadian Journal of Chemistry
JF - Canadian Journal of Chemistry
SN - 0008-4042
IS - 11
ER -