Synthesis and Characterization of Silver(I) Macromolecules Containing Macrocyclic Dithiocarbamate Ligand and Phosphines

Abstract

This study delineates the synthesis of a series of macrocyclic dinuclear metal dithiocarbamate-based complexes. The synthesis methodology encompasses the preparation of sodium uracil bis dithiocarbamate (U-DTC) by a controlled addition of carbon disulfide (CS₂) to uracil within a NaOH medium under refrigerated conditions (0–5 °C). The resultant U-DTC ligand serves as the foundation for novel Ag(I) complexes, incorporating phosphine ligands, specifically dppe and dppp, at a stoichiometric ratio of 2:1 (phosphine: metal). Additionally, complexes are formed with PPh₃ at a ratio of 4:1 (phosphine: metal). Detailed characterization through spectroscopic methodologies, including FTIR, ¹H-NMR, and ¹³C-NMR analyses, reveals the coordination mode of U-DTC with the Ag center. The spectroscopic evidence confirms the attachment of U-DTC to the silver center through a bidentate fashion, involving both sulfur atoms in a chelating manner. This synthetic approach underscores the strategic utilization of U-DTC as a precursor to engineer novel Ag(I) complexes, employing phosphine ligands in controlled ratios. The spectroscopic elucidation of the coordination mode provides crucial insights into the structural arrangement and bonding characteristics within the synthesized complexes, offering a foundation for further exploration and application of these complexes in diverse chemical contexts.