Erratum: Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications (Chem. Rev. (2010) 110: 12 (6961−7001) DOI: 10.1021/cr100085k)

Abstract

The original version of the article contained erroneously derived values of CG and related thermochemical constants in Table 1. CG is the constant used to convert reduction potentials and pKa values into bond dissociation free energies (BDFEs). The errors were due to an improper correction of the standard state for H in solution from unit mole fraction (Χ = 1) to 1 molar. For a detailed description of the correct derivation, we refer readers to section S5 of our recent J. Am. Chem. Soc. article.1 Reproduced below is a new version of Table 1 which includes corrected values of the thermochemical constants. The differences between the original and corrected CG values (ΔCG) are given in the second column of the table; the corrections range from 2 to 5 kcal mol-1. Unfortunately, since these thermochemical constants were used to derive nearly every value in the subsequent tables of the original manuscript, the reported values were typically systematically in error by several kcal mol-1. While this change affects the absolute reported values, it does not change the accuracy of the relative values reported in the same solvent. Due to the extent of this correction, we have chosen to provide a new version of the 2010 Chemical Review with completely revised tables (ref 7). This new version details the thermochemical cycles used to derive all values, as well as advancements in the field of PCET thermochemistry over the past decade, and discussions of emerging areas where it has or will become of import. We apologize for any inconvenience to authors who used the incorrect values in our original review, and we hope that our thorough and transparent update will serve as an improved guide to this area.7.