796849-81-5Relevant articles and documents
Some ruthenium complexes containing cyanocarbon ligands: Syntheses, structures and extent of electronic communication in binuclear systems
Bruce, Michael I.,Buntine, Mark A.,Costuas, Karine,Ellis, Benjamin G.,Halet, Jean-Fran?ois,Low, Paul J.,Skelton, Brian W.,White, Allan H.
, p. 3308 - 3326 (2007/10/03)
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.
