Ligand Substitution-Reactions In Paramagnetic Ruthenium(Iii) Phosphine Complexes - X-Ray Crystal-Structure Of [Methyltriphenylphosphonium] [Tetrachloro-Bis(Triphenylphosphine)-Ruthenium(Iii)]

Reaction of the tetrachlorobis(triphenylphosphine)Ru(III) anion with either 1,2-bis(diphenylphosphino)ethane (diphos) or bis(2-diphenylphosphinoethyl)phenylphosphine (triphos) in CH2Cl2 leads to the reduction of the Ru(III) centre with concomitant formation of dichlorobis(1,2-bis(diphenylphosphino)ethane)Ru(II) and dichloro(bis(2-diphenylphisphinoethyl)phenylphosphine)Ru(II), respectively. The products were characterized by P-31 NMR spectroscopy and the crystal structure of the anionic Ru(III) complex, [MePPh3][RuCl4(PPh3)2], was determined and shown to possess trans octahedral geometry. The crystals are orthorhombic, space group P2(1)2(1)2(1), with a = 10.744(3) angstrom, b = 20.875(5) angstrom, c = 21.637(6) angstrom, and V = 4832(2) angstrom3. Convergence to conventional R values of R = 0.086 and R(w) = 0.070 was obtained for 186 variable parameters and 1466 reflections with I > 2sigma(I).