Inorganic Chemistry, Vol.34, No.15, 3973-3979, 1995
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 thiolate complexes [In(SC5H4N)(3)] (1), [In(SC5H3N-3-SiMe(3))(3)] (2), and [Ga(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(NO3)(3) . xH(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(3) in ethanol solution, the binuclear species 3 and 6 are obtained. Compound 5 was prepared using GaCl3 in THF with pyridine-2-thiol under strictly anaerobic conditions. Compound 4 was prepared under anaerobic conditions in THF solvent from GaCl3 and pyridine-2-thiol, Attempts to prepare complexes of the 3,6-bis(tert-butyldimethylsilyl)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) was isolated and the structure characterized. Crystal data: 1, C15H12N3S3In, 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, C24H36N3S3Si3In, 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) Angstrom, beta = 101.83(3)degrees, V = 1429.8(7) Angstrom(3), Z = 2, 1699 reflections, R = 0.0296; 5, C15H12N3S3Ga, monoclinic, P2(1)/n, a = 8.661(2) Angstrom, b = 11.609(4) Angstrom, c = 9.315(2) Angstrom, beta = 115.40(3) Angstrom, Z = 2, 1508 reflections, R = 0.0453; 6, C24H26N4O2S4Ga2, monoclinic, P2(1)/n, a = 8.444(2) Angstrom, b = 11.479(2) Angstrom, c = 14.162(3) Angstrom, beta = 1354.4(7)degrees, Z = 2, 1513 reflections, R = 0.0349; 7, C124H248N6OS6Si12Na6, triclinic, P $($) over bar$$ 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.