The decomposition of dithiocarbamates (DTC) in primary amines have been studied for many years, as DTC metal complexes have served as single source precursors for nanocrystal synthesis. The role of primary amines in DTC decomposition is well understood and oleylamine is used as solvent and reactant in the production of many sulfur containing nanocrystals. Recently, it has been observed experimentally that the decomposition temperatures for silver and bismuth DTC complexes in oleylamine are decreased when dodecanethiol (DDT) is present as an additional solvent. Lower decomposition temperatures present an opportunity for less energy intensive nanocrystal production and better size control of nanocrystal products. Herin, we present a preliminary density functional theory (DFT) study into the decomposition mechanism of silver(I) diethyldithiocarbamate and bismuth(III) diethyldithiocarbamate in the presence of butylamine and butanethiol. The role of the thiol as a proton source, displacing ligand, and proton transfer agent are considered. One-step concerted transition states and acid catalyzed decompositions routes of DTC on and off the metal centers are compared. Preliminary activation energies and potential energy diagrams are made for the reaction coordinate. Our hope is that the insights gained for this system may be applicable to a variety of dithiocarbamate systems in use today.
