Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems

M.I. Bruce, M.A. Buntine, K. Costuas, B.G. Ellis, J-F. Halet, P.J. Low, Brian Skelton, Allan White

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15 Citations (Scopus)

Abstract

The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBul) of [Ru(NCCH2CN)(PPh3)(2)Cp]PF6 (1) gives Ru{N=C=CH(CN)}(PPh3)(2)Cp (2), which adds a second [Ru(PPh3)(2)Cp](+) unit to give [{Ru(PPh3)(2)Cp}(2)(mu-NCCHCN)](+) (3). Attempted deprotonation of the latter to give the mu-NCCCN complex was unsuccessful. Similar chemistry with tricyanomethanide anion gives Ru{N=C=C(CN)(2)}(PPh3)(2)Cp (4) and [{Ru(PPh3)(2)Cp}(2){mu-NCC(CN)CN}]PF6 (5), and with pentacyanopropenide, Ru{N=C=C(CN)C(CN)C(CN)(2)}(PPh3)(2)Cp (6) and [{Ru(PPh3)(2)Cp}(2){mu-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[mu-N=C={C(CN)=C(CN)(2)}CN]}(2) (10). The solid-state structures of 2-1 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. (C) 2004 Elsevier B.V. All rights reserved.
Original languageEnglish
Pages (from-to)3308-3326
JournalJournal of Organometallic Chemistry
Volume689
Issue number21
DOIs
Publication statusPublished - 2004

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