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https://hdl.handle.net/2440/70949
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Type: | Journal article |
Title: | Oxidative dimerization of arylalkynyl-ruthenium complexes |
Author: | Bruce, M. Burgun, A. Gendron, F. Grelaud, G. Halet, J. Skelton, B. |
Citation: | Organometallics, 2011; 30(10):2861-2868 |
Publisher: | Amer Chemical Soc |
Issue Date: | 2011 |
ISSN: | 0276-7333 1520-6041 |
Statement of Responsibility: | Michael I. Bruce, Alexandre Burgun, Frédéric Gendron, Guillaume Grelaud, Jean-François Halet and Brian W. Skelton |
Abstract: | Chemical oxidation of Ru(C≡CPh)(PPh3)2Cp with [FeCp2]PF6 affords the binuclear cationic complexes [Cp(PPh3)2Ru{=C=CHC6H4CPh=C=} Ru(PPh3)2Cp](PF6)2 (2) and [Cp(PPh3)2Ru{C≡C(C6H4)CPh=C=} Ru(PPh3)2Cp]PF6 (3) by radical coupling at sites shown to be electron-rich by DFT studies, particularly involving the acetylide Cβ and Ph Cpara atoms and, to a lesser extent, the Cp carbon atoms. Complexes 2 and 3 are related by facile deprotonation/protonation reactions. When the 4-position of the Ph group is blocked, attack by Cβ upon the Cp group occurs to give the bis(vinylidene) [Ru{=C=C(C6H4Me-4)-η-C 5H4[Ru(PPh3)2{=C=CH(C 6H4Me-4)}(PPh3)2Cp]}](PF 6)2 (4), which can be deprotonated to give [Ru{=C=C(C 6H4Me-4)-η-C5H4[Ru(PPh 3)2{C≡C(C6H4Me-4)}(PPh 3)2Cp]}]PF6 (5). Complex 4 is rapidly oxidized during workup to form [Ru{=C=C(C6H4Me)-η-C 5H4[Ru(CO)(PPh3)2]}(PPh 3)2Cp](PF6)2 (6). Single-crystal X-ray structure determinations of the salts 2, 3, and 6 are reported. © 2011 American Chemical Society. |
Rights: | Copyright © 2011 American Chemical Society |
DOI: | 10.1021/om200213z |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1021/om200213z |
Appears in Collections: | Aurora harvest 5 Chemistry and Physics publications |
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