In a previous work, a family of cobalt complexes derived from the fluorinated diphenylglyoxime ligand (�dArFgH2�) was synthesized. These complexes, [Co(dArFgH)2(py)2] (1 ) and [Co(dArFgH-BF2)2(py)2] (2 ), are variations of the extensively studied diglyoxime systems [Co(dRgBF2)2L2] (R = methyl, phenyl), which have been shown to catalyze hydrogen evolution at low overpotentials. Like these catalysts, 2  minimizes energy losses by generating hydrogen at negligible thermodynamic overpotentials in electrocatalysis experiments. Through cyclic voltammetry, it was determined that hydrogen evolution is occurring in protic solutions at the second reduction potential (-0.88 V vs. Fc/Fc+). Its precursor, 1 , was also characterized and studied as a means of better understanding the hydrogen evolution pathway in 2  since both complexes possess a similar electronic structure. This complex exhibits a similar catalytic peak at E = -0.86 V vs. Fc/Fc+. Nevertheless, the two complexes differ in their electrochemistry and suggest that the asymmetric complex 2  is a better catalyst for hydrogen evolution.

Mechanistic studies of fluorinated cobaloximes

245th National Meeting (2013)

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