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https://hdl.handle.net/2440/17939
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Type: | Journal article |
Title: | Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
Author: | Bruce, M. Buntine, M. Costuas, K. Ellis, B. Halet, J. Low, P. Skelton, B. White, A. |
Citation: | Journal of Organometallic Chemistry, 2004; 689(21):3308-3326 |
Publisher: | Elsevier Science Sa |
Issue Date: | 2004 |
ISSN: | 0022-328X 1872-8561 |
Statement of Responsibility: | Michael I. Bruce, Mark A. Buntine, Karine Costuas, Benjamin G. Ellis, Jean-Francois Halet, Paul J. Low, Brian W. Skelton and Allan H. White |
Abstract: | The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBu′) of [Ru(NCCH2Ph3)2Cp]PF6 (1) gives Ru{N=C=CH(CN)}(PPh3)2Cp (2), which adds a second [Ru(PPh3)2Cp]+ unit to give [{Ru(PPh3)2Cp}2 (μ-NCCHCN)]+ (3). Attempted deprotonation of the latter to give the μ-NCCCN complex was unsuccessful. Similar chemistry with tricyanomethanide anion gives Ru{N=C=C(CN)2} (PPh3)2Cp (4) and [{Ru(PPh3) 2Cp} 2 {μ-NCC(CN)CN}]PF6(5), and with pentacyanopropenide, Ru{N=C=C(CN)C(CN)C(CN)2} (PPh3)2Cp (6) and [{Ru(PPh3)2Cp}2 {μ-NCC(CN)C(CN)C(CN)CN}]PF6 (7). The Ru(dppe)Cp* analogues of 6 and 7 (8 and 9) were also prepared. Thermolysis of 6 (refluxing toluene, 12 h) results in loss of PPh3 and formation of the binuclear cyclic complex {Ru(PPh3) Cp[μ-N=C={C(CN)=C(CN)2}CN]}2 (10). The solid-state structures of 2-4 and 8-10 have been determined and the nature of the isomers shown to be present in solutions of the binuclear cations 7 and 9 by NMR studies has been probed using Hartree-Fock and density functional theory. © 2004 Elsevier B.V. All rights reserved. |
Keywords: | Ruthenium Cyanocarbon Redox properties Conformations DFT Electronic interactions |
Rights: | Copyright © 2004 Elsevier B.V. All rights reserved. |
DOI: | 10.1016/j.jorganchem.2004.07.030 |
Description (link): | http://www.elsevier.com/wps/find/journaldescription.cws_home/504090/description#description |
Published version: | http://dx.doi.org/10.1016/j.jorganchem.2004.07.030 |
Appears in Collections: | Aurora harvest 6 Chemistry publications |
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