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

W.M. Khairul, M.A. Fox, P.A. Schauer, D. Albesa-Jové, D.S. Yufit, J.A.K. Howard, Paul Low

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

A small series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(C≡CC6H4C≡CSiMe3)(L2)Cp′] and [Ru(C≡CC6H4C≡CC6H4R-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(Ctriple bond; length of mdashCC6H4Ctriple bond; length of mdashCC6H4OMe-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 ‘RuCt≡CC6H4’ 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.
Original languageEnglish
Pages (from-to)461-471
JournalInorganica Chimica Acta
Volume374
Issue number1
Early online date26 Feb 2011
DOIs
Publication statusPublished - 1 Aug 2011

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