REACTIVITY OF CATIONIC CARBONYL PHOSPHINE RUTHENIUM(II) COMPOUNDS

Cis(or trans)-[RuCl2(CO)(2)(PPh(3))(2)] react with two and one equival ents of AgBF4 to give the recently reported [Ru(CO)(2)(PPh(3))(2)][BF4 ](2) . CH2Cl2 (1) and novel [Ru(CO)(2)(PPh(3))(2)][BF4]. 1/2CH(2)Cl(2) (2), respectively. Cis-[RuCl2(CO)(2)(PPh(3))(2)] also reacts with two equivalents of AgBF4 in the presence of CO to give [Ru(CO)(3)(PPh(3)) (2)][BF4](2) (3). Reactions of 1 and 2 with NaOMe and CO at 1 atm prod uce the carbomethoxy species [Ru(COOMe)(2)(CO)(2)(PPh(3))(2)] (4) and [RuCl(COOMe)(CO)(2)(PPh(3))(2)] (5), respectively. Complex 4 can also be formed from the reaction of 3 with NaOMe and CO. Alternatively, 4 i s formed from cis-[RuCl2(CO)(2)(PPh(3))(2)] with NaOMe and CO at eleva ted pressure (10 atm); if these reactants are refluxed under 1 atm of CO, [Ru(CO)(3)(PPh(3))(2)] is the product. The reaction of [RuCl(CO)(3 )(PPh(3))(2)][AlCl4] with NaOMe provides an alternative route to the p reparation of 5, but the product is contaminated with [RuCl2(CO)(2)(PP h(3))(2)]. Compounds 1, 2, 4 and 5 have been characterised by IR, H-1 NMR and analysis, whilst the formulation of 3 is proposed from spectro scopic data only. This account also examines the reactivity of [Ru(CO) (2)(PPh(3))(2)][BF4](2) . CH2Cl2 with NaBH4, conc. HCl, KI and, finall y, MeCOONa in the presence of CO. The products of these reactions, nam ely cis-[RuH2(CO)(2)(PPh(3))(2)], cis-[RuCl2(CO)(2)(PPh(3))(2)], cis-[ RuI2(CO)(2)(PPh(3))(2)] and [Ru(OOCMe)(2)(CO)(2)(PPh(3))(2)], have bee n identified by comparison of their spectra with previous literature.