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The new sodium bis(1-methyl-1H-imidazol-2-ylthio)acetate, Na((S-tim)2CHCO2), has been prepared in ethanol solution using 2-mercapto- 1-methylimidazole, dibromoacetic acid and NaOH. New di- and tri-organotin(IV) derivatives have been synthesized from reaction betweenSnRnCl4-n (R = Ph, Cy and nBu, n= 2–3) acceptors and Na((S-tim)2CHCO2). Complexes of the type ((K1O-(S-tim)2CH-CO2)SnR3) and related decarboxylated species((K2N,N-(S-tim)2CH2)SnR2Cl2) have been obtained and characterized by elemental analyses, FT-IR, ESIMS and multinuclear (1H, 13C and 119Sn) NMR spectral data. The adduct ((K1O-(S-tim)2CH-CO2)Sn(H2O)(C4H9)3) was characterized by single crystal X-ray studies. The dichloromethane reaction solution of (K1O-((S-tim)2CHCO2)Sn(C6H5)3) was re-crystallized and the decarboxylated species(((S-tim)2CH2)SnCl(H2O)(C6H5)3) was obtained as a crystalline solid and characterized by X-ray crystallography.