Preparation and Reactivity of Organometallic Complexes Bearing the Fragment “Cp*Ru(CO)(PR3)” (PR3 = PMeiPr2, PEt3): Dinuclear Complexes [{Cp*Ru(CO)(PR3)}2(μ-Cl)]+ Containing Two Chiral Centers, η2-Alkene, and Other Mononuclear Complexes

Abstract

The reactions of [Cp*RuCl(CO)(PMeiPr2)] (1) and [Cp*RuCl(CO)(PEt3)] (2) with NaBAr‘4 in fluorobenzene both under argon and under dinitrogen generate the binuclear compounds [{Cp*Ru(CO)(PMeiPr2)}2(μ-Cl)][BAr‘4] (3) and [{Cp*Ru(CO)(PEt3)}2(μ-Cl)][BAr‘4] (4), respectively, which were fully characterized. The crystal structure of compound 4 is reported, showing for the first time two chiral “Cp*Ru” fragments bonded through only one bridging chloride ligand. No dinitrogen complexes or 16-electron species could be isolated. Halide abstraction from 1 using dry acetone as solvent yields the compound [Cp*Ru(CO){η1-OC(CH3)2}(PMeiPr2)][BAr‘4] (5). A range of olefins react with [Cp*RuCl(CO)(PMeiPr2)] and NaBAr‘4 furnishing the corresponding cationic η2-alkene complexes [Cp*Ru(CO)(L)(PMeiPr2)][BAr‘4] (L = C2H4, 6; H2CCHPh, 7; and H2CCHCOOCH3, 8), which are stable under argon atmosphere in solution. The crystal structure of compound 6 is also reported. Both 1 and 2 react with SnCl2 in CH2Cl2 to yield the insertion derivatives [Cp*Ru(CO)(SnCl3)(PR3)] (PR3 = PMeiPr2, 9; PEt3, 10), which have also been characterized.