Abstract
The most popular E0Ph/Ph− value is incorrect and cannot actually be obtained from the up-to-date experimental electrochemical data only. Quantum chemical calculations presented in this work showed that the accurate E0Ph/Ph− values are equal to −1.28, −1.27 and −1.84V vs. Fc+/Fc, in MeCN, DMF and THF, respectively. These were based on the reference gas-phase electron affinity for phenyl radical from the explicitly correlated coupled-cluster method (CC) and the SMD solvation free energies of Ph/Ph− at the DFT level. The differences between CC-based and purely DFT redox potentials were below 0.1V. Using a solvation model with a mixed implicit/partially explicit treatment of the coordinating solvent allowed the calculation (at the DFT level) of the standard oxidation potential of phenyllithium in THF, −0.93V vs. Fc+/Fc, which reflects a strong effect of Li+. The substitution of just one explicit molecule of ether solvent by hexamethylphosphoramide (HMPA) shifts this potential cathodically by 0.13V.
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