Chapter 2. A Transition-State Perspective of Proton-Coupled Electron Transfers

Abstract

Proton-coupled electron transfers (PCET) are emerging as an important new class of reactions. However, experimental and theoretical criteria to distinguish between these and other classes of reactions (H-atom transfers, sequential PT-ET) remain open to discussion. We punctuate the search for such criteria with simple paradigmatic examples of reactions in the gas phase and in solution. Furthermore, we use the Interacting-State Model to assess the roles of H-bonding, tunnelling, adiabaticity and electronic parameters in PCET. Finally, we introduce guidelines that may help to design productive experiments involving PCET.