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dc.contributor.authorBruce, Michael I.
dc.contributor.authorBurgun, Alexandre
dc.contributor.authorFox, Mark A.
dc.contributor.authorJevric, Martyn
dc.contributor.authorLow, Paul J.
dc.contributor.authorNicholson, Brian K.
dc.contributor.authorParker, Christian R.
dc.contributor.authorSkelton, Brian W.
dc.contributor.authorWhite, Allan H.
dc.contributor.authorZaitseva, Natasha N.
dc.identifier.citationBruce, M. I., Burgun, A., Fox, M. A., Jevric, M., Low, P. J., …, Zaitseva, N. N. (2013). Some Ruthenium Derivatives of Penta-1,4-diyn-3-one. Organometallics, 32(11), 3286-3299.en_NZ
dc.description.abstractThe 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.en_NZ
dc.publisherACS Publishingen_NZ
dc.titleSome Ruthenium Derivatives of Penta-1,4-diyn-3-oneen_NZ
dc.typeJournal Articleen_NZ

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