Preparation and properties of thiophosphinito-bridged rhodium complexes. Crystal structure of

Article abstract of DOI:10.1016/0022-328X(88)80538-2

Reaction of Ph2P(S)H with (M=Rh or Ir) yields 2 complexes.The reactions of with t-butylisocyanide, diphosphine, or carbon monoxide have been studied.Several dirhodium(II) complexes have been prepared by a two centre oxidative-addition reaction, or by exchange reactions of .A variety of related complexes is discussed.The crystal structure of has been determined by X-ray diffraction methods.It crystallizes in the triclinic space group P<*> with cell dimensions a 12.152(7), b 16.117(8), c 10.805(7) angstroem, α 90.42(4), β 112.90(3), γ 109.27(3) deg, and Z=2.The structure has been solved from diffractometer data by Patterson and Fourier methods and refined by full-matrix least-squares to R=0.0405 and R_W=0.0584 for 5149 observed reflections.In the dimeric complex two SPPh2-ligands bridge the rhodium atoms through their S and P atoms; the coordination around each metal atom is completed by a COD molecule interacting through the two olefinic bonds.The Rh-Rh distance is of 3.770(1) angstroem, ruling out the possibility of metal-metal interaction.The two Rh(1)-S(1)-P(2)-Rh(2) and Rh(1)-P(1)-S(2)-Rh(2) units are roughly planar, and the six-atom ring has a boat conformation.