Cyanide easily displaces the DMF ligands of the Mo2O2S4(DMF)3 complex as well as reacts with the disulfide ligand on the complex in a sulfur abstraction reaction. One to three DMF ligands are displaced by cyanide in the exchange reaction to potentially form several different products. The products from the exchange reaction were analyzed to determine the preferred product as (a) the products from the exchange reaction or (b) the products from a sulfur abstraction reaction. The reactivity of the sulfur abstraction reaction by cyanide with the disulfide to form thiocyanate was studied stoichiometrically as a function of pH to find strong correlation between the pH and reaction rate of thiocyanate formation. The complex was employed as a catalyst for the reaction of cyanide and thiosulfate to form thiocyanate. High conversion of cyanide to thiocyanate was achieved in a time period of 20 minutes. Reaction mechanism of the catalytic reaction was investigated experimentally and with DFT calculations. Catalytic cycle is proposed where initial step requires a sulfur abstraction reaction and thiocyanate formation. The catalyst regeneration step is proposed as well. DFT calculations were performed to analyze various regeneration steps. Potential deactivation routes of the catalytic cycle were discovered and a catalytically inactive complex isolated and characterized.

Reactivity of the Mo2O2S4(DMF)3 complex with cyanide and catalytic conversion of cyanide to thiocyanate

253rd National Meeting (2017)

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