Proton-Coupled Electron Transfer

Abstract

An initial review (PCET1) on proton-coupled electron transfer (PCET) by Huynh and Meyer appeared in Chemical Reviews in 2007. 1 This is a perennial review, a follow up on the original. It was intended for the special Chemical Reviews edition on Proton Coupled Electron Transfer that appeared in December, 2010 (Volume 110, Issue 12 Pages 6937-710). The reader is referred to it with articles on electrochemical approaches to studying PCET by Costentin and coworkers, 2 theory of electron proton transfer reactions by Hammes-Schiffer and coworkers, 3 proton-coupled electron flow in proteins and enzymes by Gray and coworkers, 4 and the thermochemistry of proton-coupled electron transfer by Mayer and coworkers. 5 Coverage for the current review is intended to be broad, covering all aspects of the topic comprehensively with literature coverage overlapping with the later references in PCET1 until late 2010. There is a growing understanding of the importance of PCET in chemistry and biology and its implications for catalysis and energy conversion. This has led to a series of informative reviews that have appeared since 2007. They include: "The possible role of Proton-coupled electron Transfer (PCET) in Water oxidation by Photosystem II" by Meyer and coworkers in 2007, 6 "Theoretical studies of proton-coupled electron transfer: Models and concepts relevant to bioenergetics" by Hammes-Schiffer and coworkers in 2008, 7 "Electrochemical Approach to the Mechanistic Study of Proton-Coupled Electron Transfer" by Costentin in 2008, 8 "Proton-Coupled Electron Transfer in Biology: Results from Synergistic Studies in Natural and Model Systems" by Nocera and Reece in 2009, 9 and "Integrating Proton-Coupled Electron Transfer and Excited States" by Meyer and coworkers in 2010. 10

Using coherence to enhance function in chemical and biophysical systems

“…Proton-coupled electron transfer is ubiquitous in biology and is also important for realizing difficult chemical transformations, including production of solar fuels 97,98 . An opportunity for coherence is in the coordination of the electron and proton transfer, where quantum effects are relevant because these are light particles.…”

Application of 1,2,3-triazolylidenes as versatile NHC-type ligands: synthesis, properties, and application in catalysis and beyond

“…Specifically, the transient proton acceptor ability enables an intramolecular transfer of protons coupled to electron transfer (proton-coupled electron transfer, PCET), which is a key concept 5 for facilitating multielectron processes that take place in water oxidation. 68 …”

Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities

“…Using Mayer's effective BDFE formalism [29], we identified a number of combinations of photocatalysts and bases which could furnish the desired carboamidation product. However, the highest yielding combination was found to be the tetrabutylammonium salt of dibutyl phosphate Bu 4 N + (BuO) 2 PO 2 − and [Ir{dF(CF 3 )ppy} 2 (bpy)]PF 6 . The reaction is demonstrated to have a broad substrate scope, tolerating electron-rich and electron-deficient arenes, as well as a number of arene substitution patterns.…”

“…'Proton-coupled electron transfer' (PCET) describes any elementary step (or series of elementary steps) in which both a proton and an electron are exchanged [1][2][3][4][5][6][7][8][9]. Within this broad definition, further distinctions may be drawn: if the proton and electron move simultaneously, the elementary step is referred to as a concerted PCET.…”