Oxidative addition of H-SiR3 to Di- and triruthenium carbonyl complexes bearing a bridging azulene ligand: Isolation of new silylruthenium complexes and catalytic hydrosilylation of ketones

Kouki Matsubara, Kazuhiro Ryu, Tomoyuki Maki, Takafumi Iura, Hideo Nagashima

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31 Citations (Scopus)

Abstract

Oxidative addition of PhMe2SiH to di- and triruthenium carbonyl clusters bearing 4,6,8-trimethylazulene as the bridging ligand was studied in relation to mechanisms of hydrosilylation of ketones catalyzed by these complexes. Reaction of PhMe2SiH with (μ355-4,6,8-trimethylazulene)Ru 3(CO)7 (3) resulted in liberation of a CO ligand, oxidative addition of the Si-H bond, and hydrogenation of one carbon-carbon double bond in the azulene ligand to form a novel 46-electron cluster, (μ235-4,5-dihydro-4,6,8-trimethy lazulene)Ru3(H)(SiMe2Ph)(CO)6 (6). In contrast, (μ235-4,6,8-trimethylazulene)Ru 2(CO)5 (4) reacted with HMe2SiPh to give (μ235-4,5-dihydro-4,6,8-trimethy lazulene)Ru2(CO)5(SiMe2Ph)2 (7), which has a unique Ru→Ru dative bond, by way of oxidative addition of two molecules of PhMe2SiH to the starting diruthenium complex followed by hydrogenation of a carbon-carbon double bond in the azulene ligand. In contrast to the fact that the diruthenium complexes 4 and 7 are not catalytically active, the triruthenium clusters 3 and 6 are catalysts for the hydrosilylation of acetophenone with moderate catalytic activity. NMR observation of intermediates in the catalytic hydrosilylation of acetophenone using 6 as catalyst suggests the existence of a reaction pathway without a cluster fragmentation, in which the triruthenium cluster is involved in the catalytic cycle.

Original languageEnglish
Pages (from-to)3023-3032
Number of pages10
JournalOrganometallics
Volume21
Issue number14
DOIs
Publication statusPublished - Jul 8 2002

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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