Some ruthenium derivatives of penta-1,4-diyn-3-one

M.I. Bruce, A. Burgun, M.A. Fox, M. Jevric, Paul Low, B.K. Nicholson, C.R. Parker, Brian Skelton, Allan White, N.N. Zaitseva

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Abstract

The reaction between Ru(C≡CH)(dppe)Cp* (1) and oxalyl chloride affords ({Ru(dppe)Cp*}C≡C)2CO (2) in 72% yield. Methylation (MeOTf) of 2 occurs first on the carbonyl oxygen, affording [({Ru(dppe)Cp*}C≡C)2C(OMe)]OTf ([3]OTf). A second methylation of [3]+ on the alkynyl Cβ proceeds slowly, affording [{Cp*(dppe)Ru}CCMeC(OMe)CC{Ru(dppe)Cp*}][OTf]2 ([4][OTf]2), whereas protonation of [3]+ occurs readily to give crystallographically characterized [{Cp*(dppe)Ru}CCHC(OMe)CC{Ru(dppe)Cp*}][OTf]2 ([5][OTf]2). The molecular structures of [3]OTf and [5][OTf]2 suggest that polarization by the CO group results in significant contributions from the alkynyl-allenylidene or alkynyl-carbyne mesomers, respectively. Reaction of 2 in refluxing MeOH containing [NH4]PF6 results in partial methanolysis to give Ru{C≡CC(O)CH═CH(OMe)}(dppe)Cp* (6). Knövenagel condensation of 2 with CH2(CN)2 affords {[Ru(dppe)Cp*]C≡C}2C═C(CN)2 (7). The related asymmetric complex {Cp*(dppe)Ru}C≡C[C═C(CN)2]C≡CC≡C{Ru(dppe)Cp*} (8) was obtained from the reaction between Ru{C≡CC(CN)═C(CN)2}(dppe)Cp* and lithiated Ru(C≡CC≡CH)(dppe)Cp*. Single-crystal structural determinations of 2, [3]OTf, [5][OTf]2, 6, 7, and 8 are reported, together with a supporting computational study of relevant electronic structures.
Original languageEnglish
Pages (from-to)3286-3299
JournalOrganometallics
Volume32
Issue number11
Early online date16 May 2013
DOIs
Publication statusPublished - 10 Jun 2013

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Bruce, M. I., Burgun, A., Fox, M. A., Jevric, M., Low, P., Nicholson, B. K., ... Zaitseva, N. N. (2013). Some ruthenium derivatives of penta-1,4-diyn-3-one. Organometallics, 32(11), 3286-3299. https://doi.org/10.1021/om400208q