Some Pentamethylcyclopentadienyl-Ruthenium Derivatives of Methyl Propiolate

M.I. Bruce, B.C. Hall, Brian Skelton, E.R.T. Tiekink, Allan White, N.N. Zaitseva

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Abstract

The reaction between methyl propiolate and RuCl(PPh3)(2)Cp* and NH4PF6 in EtOH gives cationic vinylidene [Ru{=C=CH(CO2Me)}(PPh3)2Cp*][PF6] (1), which is deprotonated to Ru(C=CCO2Me)(PPh3)(2)Cp* by NaOMe. The alkynyl complex reacts with PhCH2Br to give [Ru{=C=C(CH2Ph)(CO2Me)}(PPh3)(2)Cp*](+), isolated as its bromide and PF6- salts. In contrast, reactions between methyl propiolate and RuCl(PPh3)(2)Cp* in benzene afford neutral vinylidene RuCl{=C=CH(CO2Me)}(PPh3)Cp* (4) and metallacycle RuCl{CH=C(CO2Me)CH=C(CO2Me)}(PPh3)Cp* (5). The former complex is dehydrochlorinated by NaOMe in the presence of MeCN or P(OMe)(3) to give Ru(C=CCO2Me)(L)(PPh3)Cp* [L = MeCN and P(OMe)(3), respectively]. A minor product (2%), obtained from treatment of (5) with NaOMe, is Ru{CH=C(CO2Me)CH=C(CO2Me)C=CHC(O)OMe}(CO)(PPh3)(2) (8). X-Ray crystal structures of complexes (1), (4), (5) and (8) are reported.
Original languageEnglish
Pages (from-to)99-107
JournalAustralian Journal of Chemistry
Volume53
Issue numberN/A
DOIs
Publication statusPublished - 2000

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