Synthesis, Characterization, and Hydrogen Evolution Activity of Metallo--(4-fluoro-2,6-dimethylphenyl)porphyrin Derivatives.

Zn(II), Cu(II), and Ni(II) 5,10,15,20-tetrakis(4-fluoro-2,6-dimethylphenyl)porphyrins (TFPs) have been synthesized and characterized. The electronic spectroscopy and cyclic voltammetry of these compounds, along with the free-base macrocycle (2H-TFP), have been determined; 2H-TFP was also structurally characterized by X-ray crystallography. The Cu(II)TFP exhibits catalytic activity for the hydrogen evolution reaction (HER). The analysis of linear sweep voltammograms shows that the HER reaction of Cu(II)TFP with benzoic acid is first-order in proton concentration with an average apparent rate constant for HER catalysis of = 5.79 ± 0.47 × 10 M s.