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

A series of complexes of Ni, Cu, Zn and Cd with 3-trimethylsilylpyridi ne-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 obt ained by electrochemical oxidation of the metal in an acetonitrile sol ution 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-Me3Sipy t)] 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 bee n 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 struct ure 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 co mpounds synthesized.