CHLORONITRILE COMPLEXES OF RU(III) AND RU(IV) AND THEIR REACTIVITY TOWARDS SEVERAL LIGANDS

Two new series of anionic organonitrile compounds are described. Complexes of type I: tetraethylammonium pentachloro(nitrile)ruthenate(IV) {(NEt4)[RuCl5(RCN)]; R = Me, Ph} were prepared by the reaction of commercial 'RuCl3·3H2O' with the appropriate nitrile in the presence of NEt4Cl. Complexes of type II: tetraethylammonium tetrachlorobis(nitrile)ruthenate(III) {(NEt4)[RuCl4(RCN)2]; R = Me, Ph, o-MePh, m-MePh, CH2:CH, CH2:CH·CH2} were prepared by the reaction of 'RuCl3·3H2O' with excess of appropriate nitrile in methanol, in the presence of a stoichiometric amount of NEt4Cl (1/1). These complexes were also obtained when starting with a new ruthenium anionic complex [Ru2Cl7(OH)3]2- in the appropriate nitrile. The exceedingly labile nitriles of the complexes of type I have been substituted by N,N-dimethylformamide (DMF). Reactions of the complexes of type II with pyridine (Py) and diphenylmethylphosphine (PPh2Me) produce the compounds (NEt4)[RuCl4Py2] (IIG) and RuCl2(RCN)2(PPh2Me)2, R = o-MePh (IVA), respectively. © 1979.