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We present an update and revision to our 2010 review on the topic of protoncoupled electron transfer (PCET) reagent thermochemistry. Over the past decade, the data and thermochemical formalisms presented in that review have been of value to multiple fields. Concurrently, there have been advances in the thermochemical cycles and experimental methods used to measure these values. This Review (i) summarizes those advancements, (ii) corrects systematic errors in our prior review that shifted many of the absolute values in the tabulated data, (iii) provides updated tables of thermochemical values, and (iv) discusses new conclusions and opportunities from the assembled data and associated techniques. We advocate for updated thermochemical cycles that provide greater clarity and reduce experimental barriers to the calculation and measurement of Gibbs free energies for the conversion of X to XH n in PCET reactions. In particular, we demonstrate the utility and generality of reporting potentials of hydrogenation, E°(V vs H 2 ), in almost any solvent and how these values are connected to more widely reported bond dissociation free energies (BDFEs). The tabulated data demonstrate that E°(V vs H 2 ) and BDFEs are generally insensitive to the nature of the solvent and, in some cases, even to the phase (gas versus solution). This Review also presents introductions to several emerging fields in PCET thermochemistry to give readers windows into the diversity of research being performed. Some of the next frontiers in this rapidly growing field are coordination-induced bond weakening, PCET in novel solvent environments, and reactions at material interfaces.

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Biological redox machines require efficient transfer of electrons and holes for function. Reactions involving multiple tunneling steps, termed “hopping,” often promote charge separation within and between proteins that is essential for energy storage and conversion. Here we show how semiclassical electron transfer theory can be extended to include hopping reactions: graphical representations (called hopping maps) of the dependence of calculated two-step reaction rate constants on driving force are employed to account for flow in a rhenium-labeled azurin mutant as well as in two structurally characterized redox enzymes, DNA photolyase and MauG. Analysis of the 35 Å radical propagation in ribonucleotide reductases using hopping maps shows that all tyrosines and tryptophans on the radical pathway likely are involved in function. We suggest that hopping maps can facilitate the design and construction of artificial photosynthetic systems for the production of fuels and other chemicals.

Chemical reactions that involve net hydrogen atom transfer (HAT) are ubiquitous in chemistry and biology, from the action of antioxidants to industrial and metalloenzyme catalysis. This report develops and validates a procedure to predict rate constants for HAT reactions of oxyl radicals (RO • ) in various media. Our procedure uses the Marcus cross relation (CR) and includes adjustments for solvent hydrogen-bonding effects on both the kinetics and thermodynamics of the reactions. Kinetic solvent effects (KSEs) are included by using Ingold's model, and thermodynamic solvent effects are accounted for by using an empirical model developed by Abraham. These adjustments are shown to be critical to the success of our combined model, referred to as the CR/KSE model. As an initial test of the CR/KSE model we measured self-exchange and cross rate constants in different solvents for reactions of the 2,4,6-tri-tert-butylphenoxyl radical and the hydroxylamine 2,2′-6,6′-tetramethylpiperidin-1-ol. Excellent agreement is observed between the calculated and directly determined cross rate constants. We then extend the model to over 30 known HAT reactions of oxyl radicals with OH or CH bonds, including biologically relevant reactions of ascorbate, peroxyl radicals, and α-tocopherol. The CR/KSE model shows remarkable predictive power, predicting rate constants to within a factor of 5 for almost all of the surveyed HAT reactions.free radicals | Marcus theory | proton-coupled electron transfer | reactive oxygen species | oxyl radicals H ydrogen atom transfer (HAT) reactions (Eq. 1) have been a cornerstone of organic and biological chemistry for over a century (1, 2). These reactions are key steps in many important processes, from energy conversion to the chemistry of reactive oxygen species and antioxidants (3). Thus, developing a detailed understanding of the factors that dictate HAT reactivity has long been a goal.A large number of HAT rate constants have been measured in many laboratories with various techniques (4, 5). Rates of HAT reactions have traditionally been understood by using the BellEvans-Polanyi (BEP) relation, which relates the activation energy to the enthalpic driving force (6). Whereas the BEP relation holds well within sets of similar reactions, a comprehensive theoretical understanding of HAT is still emerging (3).Our group has been exploring the use of the Marcus cross relation (CR) Eq. 2 (7), a corollary of the Marcus theory of electron transfer, as the basis for a general model for HAT rates (8)(9)(10)(11)(12). This use of the CR grew out of recognizing HAT as one class of a larger set of reactions in which one electron and one proton are transferred (, termed proton-coupled electron transfer. In this paper, we use "HAT" to refer to any reaction in which H • is transferred from a donor to an acceptor in a single kinetic step (Eq. 1), although other definitions have been used (13).The CR, with respect to HAT reactions, relates the cross rate constant (k XH∕Y• , Eq. 1) to the two degenerate self-exchange rate c...