SYNTHESIS OF 3-TRIMETHYLSILYPYRIDINE-2-THIONE (3-ME3SIPYTH) COMPLEXES OF NICKEL, COPPER, ZINC AND CADMIUM - CRYSTAL AND MOLECULAR-STRUCTURE OF [CD(3-ME3SIPYT)2]

A series of complexes of Ni, Cu, Zn and Cd with 3-trimethylsilylpyridine-2-thione (3-Me3SipytH) as ligand has been prepared. Complexes [M(3-Me3Sipyt)2] (M=Ni(II), Zn(II) and Cd(II)) and [Cu(3-Me3Sipyt)] are obtained by electrochemical oxidation of the metal in an acetonitrile solution of the neutral ligand (3-Me3SipytH). Adducts [Ni(3-Me3Sipyt)2L] (L=2,2-bipyridine or 1,10-phenanthroline) were obtained by addition of the extra ligand to the electrolyte phase. Treatment of [Cu(3-Me3Sipyt)] with 1,2-bis(diphenylphosphino)ethane (dppe) in acetone gave [Cu2(3-Me3Sipyt)2(dppe)3]. The X-ray structure of [Cd(3-Me3Sipyt)2] has been determined: monoclinic, space group P2(1)/n, with a=11.818(1), b=13.649(1), c=13.218(1) angstrom, beta=92.00(1)degrees and Z=4. The structure was determined by direct methods and refined to R=0.030 and R(w)=0.031. In the binuclear complex each cadmium(II) centre has a trigonal bipyramidal coordination sphere with an equatorial S3 plane, involving two bridging sulfur and one terminal sulfur. The axial positions are occupied by the nitrogen atoms of two ligands. Vibrational, electronic and H-1, C-13 and P-31 NMR spectral data are presented for all the compounds synthesized.