MOLECULAR-STRUCTURE OF CHLOROTHIOMETHOXYMETHYL-BIS(TRIPHENYLPHOSPHINE)PALLADIUM(II)METHYLENECHLORIDE SOLVATE AT 160-DEGREES-C

The precise molecular structure of [PdCl(CH2SCH3)(PPh3)2] has been determined from three-dimensional X-ray diffraction data collected at -160°C. The CH2Cl2 solvated crystal ([PdCl(CH2SCH3)(PPh3)2 · CH2Cl2]) belongs to the monoclinic system, space group P21/n, with four formula units in a cell of dimensions: a 14.973(3), b 15.333(3), c 17.377(3) Å and β 115.77(1)° at -160°C. The structure was solved by the conventional heavy atom method and refined by the least-squares procedure to R = 0.035 for observed reflections. The geometry around the palladium atom is square-planar. The phosphorus atoms of the two triphenylphosphine ligands are mutually trans. The CH2SCH3 group is bonded to the palladium atom only through the PdC σ-bond and the sulfur atom is not bonded to the metal atom (PdC(1) 2.061(3), SC(1) 1.796(3), SC(2) 1.817(5), Pd⋯S 2.973(1) Å, PdC(1)S 100.64(14)° and C(1)SC(2) 101.28(18)°). The structure is in contrast to that of [PdCl(CH2SCH3)(PPh3)], in which both the carbon and sulfur atoms of the CH2SCH3 group are bonded to the palladium atom. © 1979.