Addition of Some Simple Molecules to Transition Metal-Phosphine Complex and the Crystal and Molecular Structure of Pd{(C6H5)3P}2(CS2)

From the reaction of M{(C6H5)3P}4 (M=Pd or Pt) with CS2, M{(C6H5)3P}2(CS2) has been isolated. It has been found that M{(C6H5)3P}2 also reacts with sulfur dioxide to form a novel complex, [M{(C6H5)3P}4(SO2)n]. The structure of one of these compounds, Pd{(C6H5)3·P}2(CS2), was determined by means of X-rays. Pd{(C6H5)3P}2(CS2) crystallizes in the mono-clinic system, space group P21⁄c, with four molecules in a unit cell of dimensions: a=11.55, b=19.52, c=18.38 Å and β=128°53′. The most remarkable feature of the whole structure is the coordination of CS2 to the Pd: only one of the S atoms, S(2), coordinates to the Pd, while the CS2 ligand is bent at an angle of 140°. The Pd, two P’s, S(2) and C(1) in CS2 lie approximately on the same plane. The Pd–C(1) distance of 2.00 Å is slightly shorter than the sum of the covalent radii, 2.06 Å. But the S(2)–Pd–C(1) angle of 44° is very small.