Dithiocarbamates (DTC) are bidentate organic ligands capable of binding to various metals. First synthesized in 1964, the cis-dicarbonylbis(diorganodithiocarbamato)iron(II) complex (Fe(CO)2(S2CNRR’)2) continues to provide a wealth of information regarding organometallic bonding. Recent thermogravimetric analysis (TGA) studies of several of these iron dithiocarbamates were performed in order to provide insight into the thermal decomposition of metal-DTC complexes. Depending on the nature of the dithiocarbamate ligand, these complexes appear to decompose either by the loss of both carbonyl (CO) ligands simultaneously, or by the initial loss of a single CO ligand. In both cases, the ultimate result of the thermal decomposition is the formation of iron sulfides and/or iron. Initial loss of one CO ligand implies the formation of a five-coordinate intermediate, Fe(CO)(S2CNRR’)2 and/or a bridged dimer of this five-coordinate intermediate, (Fe(CO)(S2CNRR’)2)2. TGA analysis (including FTIR of the gaseous products) following the loss of one CO ligand does not indicate the loss of a second CO ligand. In addition, thermal scan rate influences the thermal decomposition of these complexes. This work aims to further elucidate the thermal decomposition pathways of these dithiocarbamate complexes, including the effects of the ligand functional groups, thermal scan rate, and TGA purge gas. In addition, work is also underway to model the thermal decomposition mechanism of iron dithiocarbamates using density functional theory.

Investigation of the thermal decomposition of cis-dicarbonylbis(diorganodithiocarbamato)iron(II) using TGA/FTIR and density functional theory

251st National Meeting (2016)

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