Alkene purification from its common impurities is an important process in petrochemistry. Nickel bis(dithiolene) complexes were reported as electrocatalysts in this process. The mechanism for the reaction of Nickel bis(dithiolene) complexes with ethylene was studied and new catalysts were designed computationally. In 2007, the molybdenum tris(dithiolene) compounds [Mo(bdt)2(tfd)] and [Mo(tfd)2(bdt)] were synthesized to bind ethylene reversibly, generating the intraligand adduct (eq 1).1 In 2009, another rhenium tris(thiolate) complexes [Re(TTCN)]n (n=0, +1, +2) were studied to react with ethylene, where [Re(TTCN)] does not bind ethylene, [Re(TTCN)]+ binds ethylene reversibly, and [Re(TTCN)]2+ forms a stable adduct with ethylene (eq 2).2With the wB97X-D functional, the reaction mechanisms for eq 1 and eq 2 were investigated theoretically. Based on the knowledge gained in the mechanistic study, designing metal complexes that are better than the molybdenum and rhenium complexes were proposed by replacing the metals and the ligands. 1. Harrison, D. J.; Lough, A. J.; Nguyen, N.; Fekl, U. Angew. Chem. Int. Ed. 2007  , 46, 7644.2. Grapperhaus,C. A.; Ouch, K.; Mashuta, M. S. J. Am. Chem. Soc. 2009  , 131, 64.

Theoretical investigations of the mechanism for ethylene addition to metal tristhiolate complexes and catalysts design

247th National Meeting (2014)

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