Ru(II) COMPLEXES CONTAINING CHELATING PHOSPHINE LIGANDS. SYNTHESIS, CHARACTERIZATION, AND X-RAY CRYSTAL STRUCTURES OF DICHLOROBIS(1,2-BIS(DIPHENYLPHOSPHINO)ETHANE)Ru(II) AND THE COORDINATIVELY UNSATURATED TRIGONAL-BIPYRAMIDAL CATION, CHLOROBIS-(1,2-BIS(DIPHENYLPHOSPHINO)ETHANE)Ru(II)

Abstract

Abstract The reaction of trans-RuCl2(dppe)2 (1), with AgBF4 in tetrahydrofuran leads to abstraction of one of the halide ligands to produce the trigonal-bipyrimidal complex, [RuCl(dppe)2]BF4 (2). Both products are characterized by 31P NMR spectroscopy and their crystal structures determined. For the coordinatively unsaturated trigonal-bipyramidal complex (2), we found no evidence for the presence of more than one species or fluxional behaviour at room temperature in the 31P NMR spectrum. This complex was found to possess a trigonal-bipyramidal geometry in the solid state. Crystals of 1 are monoclinic, space group P21/c with a = 23.713(4)Å, b=11.156(1)Å, c = 17.595(2)Å, β=103.23(1) and v=4531(1)Å3. Convergence to conventional R values of R=0.043 and Rw = 0.042 was obtained for 416 variable parameters and 2746 reflections with I>3σ(I). Compound 2 in triclinic, P1, a=12.482(3)Å, b=12.543(3)Å, c=17.582(3)Å, α = 87.52(2)°, β= 72.70(2)° γ = 74.35(2)° and V= 2529(1)Å3. Values of R = 0.072 and Rw = 0.097 were obtained for 487 variable parameters and 3242 reflections with I>3σ(I)