Abstract

The present study investigates the synthesis, characterization, and coordination chemistry of ammonium N-(o-tolyl) dithiocarbamate (N-o-tolyl-ADTC) with Group 15 metal ions - arsenic(III), antimony(III), and bismuth(III) - across acidic, neutral, and alkaline pH conditions. The ligand, containing both nitrogen and sulphur donor atoms, can coordinate through one or both sulphur atoms. Its complexes with transition metals are well documented, but those with As(III), Sb(III), and Bi(III) are less explored. The ligand was synthesized from o-toluidine, carbon disulfide, and ammonium hydroxide, followed by purification. Comprehensive characterisation was achieved using IR, UV-Vis, and NMR spectroscopy. Complexation reactions were studied in varying pH media, and the complexes were analysed by spectroscopic methods, elemental analysis, and (where possible) single-crystal X-ray diffraction. Stability constants were determined potentiometrically and spectrophotometrically, revealing pronounced pH-dependent behaviour. Structural elucidation, supported by computational modelling, indicated bidentate coordination via the two sulphur atoms, with geometry and nuclearity varying by metal and medium. Implications for coordination chemistry, analytical applications (selective extraction/preconcentration), and environmental remediation are discussed. The study provides new insights into selective chelating agents for toxic metalloids and highlights the utility of N-aryl dithiocarbamates in analytical and environmental chemistry.

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