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Some Ruthenium Derivatives of Penta-1,4-diyn-3-one

Bruce, Michael I; Burgun, Alexandre; Fox, Mark A; Jevric, Martyn; Low, Paul J; Nicholson, Brian K; Parker Christian, R; Skelton, Brian W; White, Allan H; Zaitseva, Natasha N

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Michael I Bruce

Alexandre Burgun

Martyn Jevric

Paul J Low

Brian K Nicholson

R Parker Christian

Brian W Skelton

Allan H White

Natasha N Zaitseva


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.


Bruce, M. I., Burgun, A., Fox, M. A., Jevric, M., Low, P. J., Nicholson, B. K., …Zaitseva, N. N. (2013). Some Ruthenium Derivatives of Penta-1,4-diyn-3-one. Organometallics, 32(11), 3286-3299.

Journal Article Type Article
Publication Date Jan 1, 2013
Deposit Date Aug 13, 2013
Publicly Available Date Aug 15, 2013
Journal Organometallics
Print ISSN 0276-7333
Electronic ISSN 1520-6041
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 32
Issue 11
Pages 3286-3299


Accepted Journal Article (1.7 Mb)

Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher.

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