Models for proton-coupled electron transfer in photosystem II.

The coupling of proton and electron transfers is a key part of the chemistry of photosynthesis. The oxidative side of photosystem II (PS II) in particular seems to involve a number of proton-coupled electron transfer (PCET) steps in the S-state transitions. This mini-review presents an overview of recent studies of PCET model systems in the authors' laboratory. PCET is defined as a chemical reaction involving concerted transfer of one electron and one proton. These are thus distinguished from stepwise pathways involving initial electron transfer (ET) or initial proton transfer (PT). Hydrogen atom transfer (HAT) reactions are one class of PCET, in which H(+) and e (-) are transferred from one reagent to another: AH + B --> A + BH, roughly along the same path. Rate constants for many HAT reactions are found to be well predicted by the thermochemistry of hydrogen transfer and by Marcus Theory. This includes organic HAT reactions and reactions of iron-tris(alpha-diimine) and manganese-(mu-oxo) complexes. In PS II, HAT has been proposed as the mechanism by which the tyrosine Z radical (Y(Z)*) oxidizes the manganese cluster (the oxygen evolving complex, OEC). Another class of PCET reactions involves transfer of H(+) and e (-) in different directions, for instance when the proton and electron acceptors are different reagents, as in AH-B + C(+) --> A-HB(+) + C. The oxidation of Y(Z) by the chlorophyll P680 + has been suggested to occur by this mechanism. Models for this process - the oxidation of phenols with a pendent base - are described. The oxidation of the OEC by Y(Z)* could also occur by this second class of PCET reactions, involving an Mn-O-H fragment of the OEC. Initial attempts to model such a process using ruthenium-aquo complexes are described.