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https://hdl.handle.net/2440/68770
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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 1872-8561 |
Statement of Responsibility: | 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 Ruthenium Lithiation X-ray structure |
Rights: | Copyright © 2011 Elsevier B.V. All rights reserved. |
DOI: | 10.1016/j.jorganchem.2011.07.021 |
Published version: | http://dx.doi.org/10.1016/j.jorganchem.2011.07.021 |
Appears in Collections: | Aurora harvest 5 Chemistry and Physics publications |
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