Current study discussed the reactivity of 4,6-dimethylpyrimidine-2-thiolate towards [PtCl2(P∩P)] [(P∩P) = dppm, dppe, dppp] and their efficacy against Mycobacterium tuberculosis. The finding showed that reaction of [PtCl2(P∩P)] [(P∩P) = dppm, dppe] with sodium salt of 4,6-dimethylpyrimidine-2-thiolate yielded cis configured product [Pt{2-SC4H(4,6-Me)2N2}2(P∩P)] [(P∩P) = dppm, dppe]. However, a similar reaction with [PtCl2(dppp)] resulted in an unexpected mononuclear chelated species [Pt{SC4H(4,6-Me)2N2}2: κ-S, κ-N] formed due to the removal of phosphine ‘dppp’. An elimination of chelated phosphine is quite surprising perhaps the steric hindrance presents in the geometry of [PtCl2(dppp)] and the degree of softness in its electronic structure may attributed to rapid reactivity. All the synthesized complexes were characterized by elemental analysis, NMR (1H, 13C{1H}, 31P{1H}). The molecular structure of complex [Pt{2-SC4H(4,6-Me)2N2}2(dppe)].CH3CN (2) and [Pt{SC4H(4,6-Me)2N2}2: κ-S, κ-N] (3) was confirmed by single crystal X-ray diffraction analyses. The ligand and complexes were studied to evaluate their potential against tuberculosis strain H37RV and discussed comparative prospects between palladium and platinum complexes.