Abstract
Free-base meso-tetra(pentafluorophenyl)porphyrin, 1, is electrocatalytically active for hydrogen gas generation in the presence of p-toluenesulfonic acid. The electrochemical potential of hydrogen evolution (-1.31 V vs. Fc/Fc(+) in THF) is comparable to those of metal containing electrocatalysts such as metallated porphyrins or other metallated macrocycles. Combining experimental observations and DFT computations, we propose the most favorable hydrogen generation mechanism to be a (1) reduction, (2) protonation, (3) reduction, (4) protonation (E-P-E-P) pathway.