131344-99-5Relevant academic research and scientific papers
Chiral and Achiral Diphosphine Complexes of Ruthenium(II) Incorporating Labile Nitrile Ligands: Synthesis and Solution Chemistry of Mono- and Dinuclear Derivatives of Ru2Cl4(PP)2 (PP = Chelating Diphosphine)
Fogg, Deryn E.,James, Brian R.
, p. 1961 - 1966 (2008/10/09)
A family of nitrile complexes has been prepared by reaction of Ru2Cl4(PP)2 or RuCl2(PP)(PPh3) (PP = Ph2P(CH2)4-PPh2 (dppb), Ph2PCH2CHOCMe2OCHCH2PPh2 (diop), 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap)) with MeCN or PhCN, the product formed depending strongly on the reaction conditions. At high nitrile concentrations, the principal species present is RuCl(PP)(RCN)3+X- (X = Cl); the cation can generally be isolated (as the PF6 salt) by abstraction of the chloride counterion with NH4PF6. Use of 2 equiv of NH4PF6 generates Ru(PP)(RCN)42+(PF6-)2 (PP = dppb). In the absence of a halide-abstracting agent, addition of hexanes or diethyl ether precipitates neutral RuCl2(PP)(RCN)2 species, which undergo further loss of nitrile in the solid state (R = Me) or in solution (R = Me, Ph). Redissolution of the neutral species in chlorocarbon solvents gives Ru2Cl3(PP)2(RCN)2+X - (X = Cl) and, in benzene, Ru2Cl4(PP)2(RCN). The dinuclear cation (X = PF6) is also accessible by reaction of RuCl(PP)(RCN)3+PF6- with CH2Cl2 or CDCl3, while the mononitrile can be obtained directly by reaction of Ru2Cl4(PP)2 or RuCl2(PP)(PPh3) with small amounts of nitrile in benzene.
