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 k
app = 5.79 ± 0.47 × 103 M–1 s–1.