Diolefin and carbonyl rhodium(I) and iridium(I) complexes with phosphine sulphide ligands. Crystal structure of ClO4

Article abstract of DOI:10.1016/0022-328X(89)85053-3

The preparation and properties of new diolefinic or carbonyl cationic rhodium and iridium complexes with phosphine sulphide ligands of the type ⁿ⁺_n or ⁿ⁺_n (n=1 or 2) (L=Me3PS, Et3PS and Ph3PS, L2= Me2P(S)(S)PMe2, Et2P(S)(S)PEt2 and Ph2P(S)(S)PPh2) are described.The complexes have been characterized by elemental analyses, IR spectra, conductance studies and 31P NMR spectroscopy.Oxidative addition of I2 gives IrIII complexes.Diolefinic complexes with phosphine sulphide are catalyst precursors in the homogeneous hydrogenation of olefins.The crystal structure of ClO4 has been determined b X-ray diffraction methods.The crystal are monoclinic, space group P2₁/c with a 12.754(1), b 13.333(1), c 13.637(1) Angstroem, β 95.30(1)^o, Z=4.The cationic complex ⁺ is monomeric, with the Rh atom showing a slightly distorted square-planar environment.The cyclooctadiene ligand is coordinated to the metal through its two olefinic bonds a bis(diethylphosphine)disulphide group, bonded through its two S atoms, acts as a bidentate chelating ligand.