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

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

SUBMITTER: Warren JJ 

PROVIDER: S-EPMC3593309 | biostudies-literature | 2013 Feb

REPOSITORIES: biostudies-literature