Three methods have been developed to prepare gallium and indium complexes 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 = C10H22ClInN2S2, 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) Angstrom, b = 11.679(3) Angstrom, c = 24.238(9) Angstrom, V = 3449.7 (17) Angstrom(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 solvents such as acetonitrile, for certain molecules, two metal-ligand complexes are observed Similarly, two metal-ligand complexes are seen in NMR data taken in 80% acetonitrile/20% D2O (pD = 4.6) mixture. HPLC studies (acetonitrile/50 mM sodium acetate, pH = 4.6) show that the lipophilicity of the ligand determines the retention time of the complex.