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Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
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| Authors: | Michael I. Bruce Mark A. Buntine Benjamin G. Ellis Paul J. Low Brian W. Skelton |
| Affiliation: | a Department of Chemistry, University of Adelaide, Adelaide, SA 5005, Auatralia b LCSIM UMR CNRS 6511, Institut de Chimie, Université de Rennes 1, 35042, Rennes Cedex, France c Department of Chemistry, University of Durham, South Road, Durham DH1 3LE, England d Department of Chemistry, University of Western Australia, Crawley, WA 6009, Australia |
| Abstract: | The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBut) of [Ru(NCCH2CN)(PPh3)2Cp]PF6 (1) gives Ru{N CCH(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{NCC(CN)2}(PPh3)2Cp (4) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)CN}]PF6 (5), and with pentacyanopropenide, Ru{NCC(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-NC{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. |
| Keywords: | Ruthenium Cyanocarbon Redox properties Conformations DFT Electronic interactions |
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