The reactions of (eta(5)-C5H5)(2) MCl2 (M = Ti, Zr, or Hf) with mercaptoazoles (LH2), namely, bis(mercaptotriazoles), bis(mercaptooxadiazoles), and bis(mercaptothiadiazoles) in 2 : 1 molar ratio, respectively, have been studied in dry tetrahydrofuran in the presence of n-butylamine and the binuclear complexes of the type [{(eta-C5H5)(2) M}(2)( L)] (M = Ti/Zr/Hf) are obtained. Tentative structural conclusions are drawn for the reaction products based upon elemental analysis, electrical conductance, magnetic moment, and spectral data (UV-Vis, IR, H-1 NMR, and C-13 NMR). FAB-mass spectra of few complexes of each series were also carried out to confirm the binuclear structures. Studies were conducted to assess the growth-inhibiting potential of the complexes synthesized, and the ligands against various fungal and bacterial strains.