Long-Range Proton-Coupled Electron-Transfer Reactions of Bis(imidazole) Iron Tetraphenylporphyrins Linked to Benzoates

Concerted proton–electron transfer (CPET) reactions in iron carboxytetraphenylporphyrin complexes have been investigated using both experimental and theoretical methods. Synthetic heme models abstract H + and e – from the hydroxylamine TEMPOH or an ascorbate derivative, and the kinetics of the TEMPOH reaction indicate concerted transfer of H + and e – . Phenylene linker domains vary the electron donor/acceptor separation by approximately 4 Å. The rate data and extensive molecular simulations show that the electronic coupling decay constant (β) depends on conformational flexibility and solvation associated with the linker domain. Our best estimate of β is 0.23 ± 0.07 Å –1, a value that is near the low end of the range (0.2–0.5 Å –1 ) established for electron-transfer reactions involving related linkers. This is the first analysis of β for a CPET reaction.