GALLIUM AND INDIUM COMPLEXES OF BIS(AMINO THIOL) (N2S2) LIGANDS

Three methods have been developed to prepare gallium and indium comple xes of three tetradentate N2S2 ligands of the general formula M(N2S2)R (M = Ga, In; R = Cl, Br, SCN, O2CC6H5-O,O'). The ancillary ligand (Cl , SCN, O2CC6H5-O,O') was varied with the tetradentate ligand BAT-TM. X -ray crystallography shows that the coordination geometry about the d( 10) metal ion is influenced by the steric requirements of the ligands. X-ray crystallography of four molecules results in the following data : GaCl(BAT-TM) (1), formula = C10H22ClGaN2S2, space group = Pnma, a = 12.387(4) Angstrom, b = 21.116(6) Angstrom, c = 5.986(2) Angstrom, V = 1565.8(9) Angstrom(3), Z = 4; InCl(BAT-TM (2) formula = C10H22ClInN2S 2, space group = Pnma, a = 12.968(9) Angstrom, b = 29.29(1) Angstrom, c = 5.866(2) Angstrom, V = 1620(2) Angstrom(3), Z = 4; InNCS(BAT-TM (3 ), formula = C11H24ClInN3S3, space group = Pbca, a = 11.812(3) Angstro m, b = 11.679(3) Angstrom, c = 24.238(9) Angstrom, V = 3449.7 (17) Ang strom(3), Z = 8; In(O,O'-O2CC6H5)(BAT-TM) (4), formula C19H29O2InN2S2 space group = P2(1)/n, a = 10.783(2) Angstrom, b = 18.708(4) Angstrom, c = 12.335(4) Angstrom, V = 2321.7(9) Angstrom(3), Z = 4. Proton NMR studies show that the complexes are stable in solution; in polar solve nts such as acetonitrile, for certain molecules, two metal-ligand comp lexes are observed Similarly, two metal-ligand complexes are seen in N MR data taken in 80% acetonitrile/20% D2O (pD = 4.6) mixture. HPLC stu dies (acetonitrile/50 mM sodium acetate, pH = 4.6) show that the lipop hilicity of the ligand determines the retention time of the complex.