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Ligand redox non-innocent behaviour in ruthenium complexes of ethynyl tolans

Khairul, WM; Fox, MA; Schauer, PA; Albesa-Jove, D; Yufit, DS; Howard, JAK; Low, PJ

Authors

WM Khairul

PA Schauer

D Albesa-Jove

DS Yufit

JAK Howard

PJ Low



Abstract

A small series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(CCC6H4CCSiMe3)(L2)Cp′] and [Ru(CCC6H4CCC6H4R-4)(L2)Cp′] (R = OMe, Me, CO2Me, NO2; L2 = (PPh3)2, Cp′ = Cp; L2 = dppe; Cp′ = Cp∗) have been synthesised. One-electron oxidations of these complexes gave the corresponding radical cations, which were significantly more chemically stable in the case of the Ru(dppe)Cp∗ derivatives. The representative complex [Ru(CCC6H4CCC6H4OMe-4)(dppe)Cp∗] was further examined by spectroelectrochemical (IR and UV–Vis–NIR) methods. The results of the spectroelectrochemical studies, supported by DFT calculations, indicate that the hole is largely supported by the ‘RuCCC6H4’ moiety in a manner similar to that described previously for simple aryl ethynyl complexes, rather than being more extensively delocalized along the entire conjugated ligand.

Citation

Khairul, W., Fox, M., Schauer, P., Albesa-Jove, D., Yufit, D., Howard, J., & Low, P. (2011). Ligand redox non-innocent behaviour in ruthenium complexes of ethynyl tolans. Inorganica Chimica Acta, 374(1), 461-471. https://doi.org/10.1016/j.ica.2011.02.043

Journal Article Type Article
Publication Date Aug 1, 2011
Deposit Date Dec 14, 2011
Journal Inorganica Chimica Acta
Print ISSN 0020-1693
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 374
Issue 1
Pages 461-471
DOI https://doi.org/10.1016/j.ica.2011.02.043

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