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Carbon−Sulfur and Carbon−Phosphorus Bond Cleavage and Subsequent Carbon−Carbon Bond Formation Promoted by an Active Ruthenium(0) Species

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posted on 2002-11-12, 00:00 authored by Hiroyuki Kawano, Hayato Narimatsu, Daisuke Yamamoto, Keiichi Tanaka, Katsuma Hiraki, Masayoshi Onishi
Reaction of RuH2(CO)(PPh3)3 (1) with thiophene in the presence of styrene gives the novel diruthenium complex (Ph3P)(OC)Ru(μ-(1Z,3Z)-PhCHCHCHCHS)(μ-PPh2)Ru(CO)(PPh3) (2) with a unique bridging 4-phenyl-1,3-butadienethiolato moiety made up of the 1-thiapenta-2,4-dien-1,5-diyl and phenyl groups, which are derived from the thiophene and triphenylphosphine, respectively. Treatment of 2 on a preparative thin-layer chromatography plate of alumina or silica gel causes ZE isomerization of the bridging moiety to give (Ph3P)(OC)Ru(μ-(1Z,3E)-PhCHCHCHCHS)(μ-PPh2)Ru(CO)(PPh3) (5). The molecular structures of 2 and 5 have been determined by X-ray structure analyses.