Thermal decomposition of cis-dicarbonylbis(diorganodithiocarbamato)iron(II) complexes usually proceeds with the loss of the carbonyl ligands followed by decomposition of dithiocarbamate ligands. The mass loss assigned to the two carbon monoxide ligands sometimes occurs simultaneously and sometimes stepwise. A stepwise loss would suggest either the formation of a five-coordinate intermediate, Fe(CO)(S2CNRR')2, or some sort of bridged complex, [Fe(CO)(S2CNRR')2]2, which might be stable kinetically in the solid state. Recently, the thermal decomposition of cis-dicarbonylbis(diorganodithiocarbamato)iron(II) was re-examined using FTIR to investigate the gaseous decomposition products. Based on this research, there is reason to believe the second mass loss for the methylphenyl derivative may not correspond to the loss of the second CO. Simultaneous FTIR and TGA analysis of the decomposition of tris (diorganodithiocarbamato)iron(III) complexes and their corresponding cis-dicarbonylbis(diorganodithiocarbamato)iron(II) analogs indicate a loss of organoisothiocyanate and carbon disulfide during the decomposition of the dithiocarbamate as well as carbon monoxide for the dicarbonyl.

Comparison of thermal decomposition routes of tris (diorganodithiocarbamato)iron (III) and its dicarbonyl analog using TGA and FTIR

247th National Meeting (2014)

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