Insertion reactions of dimethyl acetylenedicarboxylate with alkenylruthenium complexes of the type [Ru(CO)Cl(R′CCHR)(PPh<inf>3</inf>)<inf>2</inf>]. The crystal structure of [Ru(CO)Cl{MeOOCCC(CO<inf>2</inf>Me)-CHCHCMe<inf>3</inf>}(PPh<inf>3</inf>)<inf>2</inf>]

M. R. Torres, A. Vegas, A. Santos, J. Ros

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Abstract

Reactions between alkenylruthenium complexes of the type [Ru(CO)Cl(R′ CCHR)(PPh3)2] (R′ = R = H, Me, Ph; R′ = H, R = C3H7, CMe3, Ph) with dimethylacetylenedicarboxylate give mixed bis-insertion complexes of formula [Ru(CO)Cl{MeOOCCC(CO2Me)CR′ CHR}(PPh3)2], which have been isolated and characterized only in the case of terminal alkyne derivatives (R′ = H). This reaction is competitive with the simple displacement reaction of the non-activated acetylene by dimethyl acetylene-dicarboxylate. The complexes were characterized by elemental analysis and 1H NMR and IR spectroscopy. The molecular structure of [Ru(CO)Cl{MeOOCCC(CO2Me)CHCHCMe3})2], determined by X-ray diffraction, can be regarded as a distorted octahedral species, in which the butadienyl ligand acts as bidentate through an additional CO Ru bond involving a carboxylate oxygen atom, the atom pairs (P,P), (Cl,C) and (O,C) being in trans positions. © 1987.
Original languageEnglish
Pages (from-to)413-421
JournalJournal of Organometallic Chemistry
Volume326
Issue number3
DOIs
Publication statusPublished - 9 Jun 1987

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