SYNTHESIS AND CHARACTERIZATION OF GALLIUM AND INDIUM THIOLATE COMPLEXES - CRYSTAL AND MOLECULAR-STRUCTURES OF [M(SC5H4N)(3)] (M=GA, IN), [IN(SC5H3N-3-SIME(3))(3)], AND [M(2)(OC2H4)(2)(SC5H4N)(4)] (M=GA, IN)

The synthesis and characterizations of the monomeric group III thiolat e complexes [In(SC5H4N)(3)] (1), [In(SC5H3N-3-SiMe(3))(3)] (2), and [G a(SC5H4N)(3)] (5) and of the binuclear alkoxy-bridged derivatives [M(2 )(OC2H5)(2)(SC5H4N)(4)] (M = In (3), Ga (6)) are described. Compounds 1 and 2 are formed in the reaction of the appropriate nitrate salt M(N O3)(3) . xH(2)O with the pyridine-2-thiol derivative in ethanol or wat er in the presence of triethylamine. In contrast, when the reaction is carried out under strictly anaerobic conditions, using the appropriat e metal chloride MCl(3) in ethanol solution, the binuclear species 3 a nd 6 are obtained. Compound 5 was prepared using GaCl3 in THF with pyr idine-2-thiol under strictly anaerobic conditions. Compound 4 was prep ared under anaerobic conditions in THF solvent from GaCl3 and pyridine -2-thiol, Attempts to prepare complexes of the 3,6-bis(tert-butyldimet hylsilyl)pyridine-2-thiol ligand type were unsuccessful. However, the sodium salt [Na{SC5H2N-3,6-(SiMe(2)Bu(t))(2)}](6) . 2(C2H5)(2)O (7) wa s isolated and the structure characterized. Crystal data: 1, C15H12N3S 3In, monoclinic, P2(1), a = 8.779(2) Angstrom, b = 11.614(2) Angstrom, c = 9.397(2) Angstrom, beta = 114.67(3)degrees, V = 870.7(4) Angstrom (3), Z = 2, 2392 reflections with I-0 > 3 sigma(I-0), R = 0.0338; 2, C 24H36N3S3Si3In, orthorhombic, Pca2(1), a = 11.645(2) Angstrom, b = 19. 741(4) Angstrom, c = 14.040(3) Angstrom, V = 3227(2) Angstrom(3), Z = 4, 1930 reflections, R = 0.0464; 3, C24H26N4O2S4In2, monoclinic, P2(1) /n, a = 8.420(2) Angstrom, b = 11.860(2) Angstrom, c = 14.629(3) Angst rom, beta = 101.83(3)degrees, V = 1429.8(7) Angstrom(3), Z = 2, 1699 r eflections, R = 0.0296; 5, C15H12N3S3Ga, monoclinic, P2(1)/n, a = 8.66 1(2) Angstrom, b = 11.609(4) Angstrom, c = 9.315(2) Angstrom, beta = 1 15.40(3) Angstrom, Z = 2, 1508 reflections, R = 0.0453; 6, C24H26N4O2S 4Ga2, monoclinic, P2(1)/n, a = 8.444(2) Angstrom, b = 11.479(2) Angstr om, c = 14.162(3) Angstrom, beta = 1354.4(7)degrees, Z = 2, 1513 refle ctions, R = 0.0349; 7, C124H248N6OS6Si12Na6, triclinic, P $($) over ba r$$ 1, a = 16.156(3) Angstrom, c = 17.665(4) Angstrom, alpha = 118.47( 3)degrees, beta = 92.40(3)degrees, gamma = 114.75(3)degrees, V = 3757( 2) Angstrom(3), Z = 1, 5125 reflections, R = 0.0809.