Facile decarboxylation of propiolic acid on a ruthenium center and related chemistry

J.H. Bowie, M.I. Bruce, M.A. Buntine, A.S. Gentleman, D.C. Graham, Paul Low, G.F. Metha, C. Mitchell, C.R. Parker, Brian Skelton, Allan White

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Abstract

Spontaneous decarboxylation of RC≡CCO2H (R = H, Ph) occurs in reactions with RuCl(PP)Cp (PP = (PPh3)2, dppe) to give [Ru(═C═CHR)(PP)Cp]+. Computational studies (DFT) of possible decarboxylation mechanisms suggest that the reaction that leads to extrusion of CO2 and formation of [Ru(═C═CH2)(dppe)Cp]+ most likely occurs by initial interaction of the anion HC≡CCO2– with RuCl(dppe)Cp by coordination of carboxylate to Ru, followed by formation of an η2-alkyne intermediate which rearranges to the η1-ethynyl species with loss of CO2. Protonation of the ethynyl group affords the parent vinylidene. In contrast, reactions of HC≡CCO2R (R = Me, Et) with RuCl(PP)Cp and [NH4]PF6 in MeOH have given [Ru{═C(OMe)CH2(CO2R)}(PP)Cp]+, formed by attack of MeOH at Cα of the intermediate vinylidenes [Ru{═C═CH(CO2R)}(PP)Cp]+. Deprotonation of the carbenes affords Ru{C(OMe)═CH(CO2R)}(PP)Cp as mixtures of cis and trans isomers. The vinylidenes, which are obtained directly from RuCl(PP)Cp and HC≡CCO2R in the presence of [NH4]PF6 in ButOH, can be deprotonated (Na/PriOH) to the corresponding alkynyls. Attempted deprotonation of [Ru(═C═CH2)(dppe)Cp]+ with LiBu gave the binuclear cyclobutenylidinium complex [{Ru(dppe)Cp}2(μ-C4H3)]+. The X-ray diffraction molecular structures of [{Ru(dppe)Cp}2(μ-C4H3)]PF6 (11), [Ru{═C(OMe)CH2(CO2Me)}(dppe)Cp]PF6 (13), Ru{C(OMe)═CH(CO2R)}(dppe)Cp (R ═ Me (15), Et (16)) and Ru(C≡CCO2R)(dppe)Cp (R = Me (21), Et (22)) are described.
Original languageEnglish
Pages (from-to)5262-5273
JournalOrganometallics
Volume31
Issue number15
Early online date1 Aug 2012
DOIs
Publication statusPublished - 2012

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Bowie, J. H., Bruce, M. I., Buntine, M. A., Gentleman, A. S., Graham, D. C., Low, P., ... White, A. (2012). Facile decarboxylation of propiolic acid on a ruthenium center and related chemistry. Organometallics, 31(15), 5262-5273. https://doi.org/10.1021/om300157w