Determining Proton-Coupled Standard Potentials and X-H Bond Dissociation Free Energies in Nonaqueous Solvents Using Open-Circuit Potential Measurements.

Proton-coupled electron transfer (PCET) reactions are increasingly being studied in nonaqueous conditions, where the thermochemistry of PCET substrates is largely unknown. Herein, we report a method to obtain electrochemical standard potentials and calculate the corresponding bond dissociation free energies (BDFEs) of stable PCET reagents in nonaqueous solvents, using open-circuit potential (OCP) measurements. With this method, we measure PCET thermochemistry in acetonitrile and tetrahydrofuran for substrates with O-H and N-H bonds that undergo 1e-/1H+ and 2e-/2H+ redox processes. We also report corrected thermochemical values for the 1/2H2(g)/H•1M and H+/H• (CG) couples in several organic solvents. For 2e-/2H+ couples, OCP measurements provide the multielectron/multiproton standard potential and the average of the two X-H BDFEs. In contrast to traditional approaches for calculating BDFEs from electrochemical measurements, the OCP method directly measures the overall PCET reaction thermodynamics and avoids the need for a pKa scale in the solvent of interest. Consequently, the OCP approach yields more accurate thermochemical values and should be general to any solvent mixture compatible with electrochemical measurements. The longer time scale of OCP measurements enables accurate thermochemical measurements for redox couples with irreversible or distorted electrochemical responses by cyclic voltammetry, provided the PCET reaction is chemically reversible. Recommendations for successful OCP measurements and limitations of the approach are discussed, including the current inability to measure processes involving C-H bonds. As a straightforward and robust technique to determine nonaqueous PCET thermochemistry, these OCP measurements will be broadly valuable, with applications ranging from fundamental reactivity studies to device development.