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https://hdl.handle.net/2440/79808
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Type: | Journal article |
Title: | Some ruthenium derivatives of penta-1,4-diyn-3-one |
Author: | Bruce, M. Burgun, A. Fox, M. Jevric, M. Low, P. Nicholson, B. Parker, C. Skelton, B. White, A. Zaitseva, N. |
Citation: | Organometallics, 2013; 32(11):3286-3299 |
Publisher: | Amer Chemical Soc |
Issue Date: | 2013 |
ISSN: | 0276-7333 1520-6041 |
Statement of Responsibility: | Michael I. Bruce, Alexandre Burgun, Mark A. Fox, Martyn Jevric, Paul J. Low, Brian K. Nicholson, Christian R. Parker, Brian W. Skelton, Allan H. White, and Natasha N. Zaitseva |
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. © 2013 American Chemical Society. |
Rights: | © 2013 American Chemical Society |
DOI: | 10.1021/om400208q |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1021/om400208q |
Appears in Collections: | Aurora harvest Chemistry publications |
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