Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC5H4N)3] (M = Ga, In), [In(SC5H3N-3-SiMe3)3], and [M2(OC2H5)2(SC5H4N)4] (M = Ga, In)

The synthesis and characterizations of the monomeric group III thiolate complexes [In(SC{sub 5}H{sub 4}N){sub 3}](1), [In(SC{sub 5}H{sub 3}N-3-SiMe{sub 3}){sub 3}](2), and [Ga(SC{sub 5}H{sub 4}N){sub 3}] (5) and of the binuclear alkoxy-bridged derivatives [M{sub 2}(OC{sub 2}H{sub 5}){sub 2}(SC{sub 5}H{sub 4}N){sub 4}] (M=In (3), Ga (6)) are described. Compounds 1 and 2 are formed in the reaction of the appropriate nitrate salt M(NO{sub 3}){sub 3}{center_dot}xH{sub 2}O with the pyridine-2-thiol derivative in ethanol or water in the presence of triethylamine. In contrast, when the reaction is carried out under strictly anaerobic conditions, using the appropriate metal chloride MCl{sub 3} in ethanol solution, the binuclear species 3 and 6 are obtained. Compound 5 was prepared using GaCl{sub 3} in THF with pyridine-2-thiol under strictly anaerobic conditions. Compound 4 was prepared under anaerobic conditions in THF solvent from GaCl{sub 3} and pyridine-2-thiol. Attempts to prepare complexes of the 3,6-bis(tertbutyldimethylsilyl)pyridine-2-thiol ligand type were unsuccessful. However, the sodium salt [Na(SC{sub 5}H{sub 2}N-3,6-(SiMe{sub 2}Bu{sup 1}){sub 2})]{sub 6}{center_dot}2(C{sub 2}H{sub 5}){sub 2}O (7) was isolated and the structure characterized.