SYNTHESIS, CHARACTERIZATION, AND REACTIVITY OF GROUP-12 METAL THIOCARBOXYLATES, M(SOCR)(2)LUT(2) [M=CD, ZN R=CH3, C(CH3)(3), LUT EQUALS 3,5-DIMETHYLPYRIDINE (LUTIDINE)]

A series of group 12 metal thiocarboxylate species. M(SOCR)(2)Lut(2) [ M = Cd, Zn; R = CH3, C(CH3)(3); Lut = 3,5-dimethylpyridin (lutidine)], were synthesized to investigate their potential to act as precursors for the formation of metal sulfide materials. These species were expec ted to undergo thiocarboxylic anhydride elimination to give stoichiome tric metal sulfides and remove the organic supporting ligands cleanly. These species were characterized by H-1, C-13, and (where appropriate ) Cd-113 NMR spectroscopies; TGA, elemental analysis, and single-cryst al X-ray diffraction. The spectroscopic and analytical data were consi stent with the formulas identified above, and in the solid state the c ompounds are monomeric with approximate tetrahedral metal coordination environments and monodentale S-bond thiocarboxylate ligands. Crystal data for Cd(SOCCH3)(2)Lut(2): crystallized in the triclinic space grou p P (1) over bar, with a = 8.267(1) Angstrom, b = 9.467(1) Angstrom, c = 14.087(1) Angstrom, alpha = 94.04(1)degrees, beta = 91.49(1)degrees , gamma 104.03(1)degrees, and Z = 2. Thermal decomposition of these co mpounds in the solid state or in solution resulted in formation of the corresponding metal sulfide at low temperatures, as seen by powder X- ray diffraction. Evidence for thiocarboxylic anhydride elimination was documented by NMR in solution phase reactions, The effects on thiocar boxylic anhydride elimination, resulting from varying M, R,pr solvent media, were examined by heating NMR tube solutions of M(SOCR)(2)Lut(2) in pyridine or toluene. Heating toluene or pyridine solutions of Cd-( SOCCH3)(2)Lut(2) resulted in formation df nanocrystalline, sphalerite CdS, as determined by X-ray diffraction and TEM. These preliminary rea ctivity studies have revealed the great potential of this highly tailo rable chemical system as precursors to group 12 metal sulfido species.