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Type: Journal article
Title: Lithiation of diynyl-ruthenium complexes: routes to novel metallated functional diynes
Author: Bruce, M.
Scoleri, N.
Skelton, B.
Citation: Journal of Organometallic Chemistry, 2011; 696(22):3473-3482
Publisher: Elsevier Science Sa
Issue Date: 2011
ISSN: 0022-328X
Statement of
Michael I. Bruce, Nancy Scoleri, Brian W. Skelton
Abstract: Conditions for the efficient lithiation of the diynyl group in complexes Ru(CCCCH)(PP)Cp′ [(PP)Cp′ = (dppe)Cp (*) 1, (PPh 3)2Cp 2 have been investigated. Addition of two equiv. LiBu to the diynyl complexes in thf solution at -78°C effects rapid conversion to putative Ru(CCCCLi)(PP)Cp′. Assays using subsequent reactions with either SiClMe3 or AuCl(PPh3) indicate that up to 80% conversion can be achieved. Reactions of the lithiated species with organic electrophiles [MeI, MeC(O)Cl, PhC(O)Cl, ClC(O)OMe, PhCHO, Ph 2CO and metal-containing substrates [MClPh3 (M = Ge, Sn), trans-RhCl(CO)(PPh3)2, cis-PtCl2(PPh 3)2, CuCl(PPh3), (AuCl)2(μ-dppm) proceed to give functionalised diynyl complexes or bimetallic derivatives which are accessible only with difficulty or not at all from the parent diynes. Single-crystal X-ray diffraction molecular structures of Ru(CCCCR)(dppe)Cp (*) (R = Me, GePh3) are reported: there is significantly greater delocalisation along the Ru-C4-R chain in the GePh 3 derivative. © 2011 Elsevier B.V. All rights reserved.
Keywords: Diynyl
X-ray structure
Rights: Copyright © 2011 Elsevier B.V. All rights reserved.
DOI: 10.1016/j.jorganchem.2011.07.021
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