Abstract
Concerted proton-electron transfer (CPET) reactions in iron carboxy-tetraphenylporphyrin 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.
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