Publication 732

J. Am. Chem. Soc. , 135 (38), 14359-14366, 2013 DOI:10.1021/ja406712c
Proton-coupled electron transfers: pH-dependent driving forces? Fundamentals and artifacts

Université Paris Diderot, Sorbonne Paris Cité, Laboratoire d’Electrochimie Moléculaire, Unité Mixte de Recherche Université - CNRS no. 7591, Bâtiment Lavoisier, 15 rue Jean de Baïf, 75205 Paris Cedex 13, France

Besides its own interest, tryptophan oxidation by photogenerated Ru complexes is one of the several examples where concerted proton–electron transfer (CPET) to water as proton acceptor endowed with a pH-dependent driving force has been invoked to explain the data. Since this notion is contrary to the very basic principles of chemical physics, it was interesting to attempt uncovering the source of this contradiction with an easily accessible substrate. Careful examination of the oxidation of the tryptophan (ethyl ester derivative) bearing a NH₃⁺/NH₂ group showed that there is no trace of such an unconventional H₂O-CPET with a pH-dependent driving force. The reaction mechanism simply consists, with both the NH₃⁺ acid and NH₂ basic forms of the tryptophan derivative, in a rate-determining electron-transfer step followed by deprotonation steps. The same is true with the ethyl ester-methyl amide derivative of tryptophan, whose behavior is even simpler since the molecule does not bear an acid–base group. No such unconventional H₂O-CPET was found with phenol, another easily accessible substrate. It may thus be inferred that the same applies to less easily available systems in which electron transfer occurs intramolecularly. These observations help to rid the road of such artificial obstacles and improve present models of H₂O-CPET reactions, a landmark towards the understanding of the role of water chains in natural systems.