TY - JOUR

T1 - Prediction of the standard potentials for one-electron oxidation of N,N,N',N' tetrasubstituted p-phenylenediamines by calculation

AU - Andersen, Cecilie L.

AU - Lacerda Junior, Evanildo Gomes

AU - Christensen, Jørn Bolstad

AU - Sauer, Stephan P. A.

AU - Hammerich, Ole

PY - 2021/9/22

Y1 - 2021/9/22

N2 - The formal potentials for the reversible one-electron oxidation of N,N,N',N' tetrasubstituted p-phenylenediamines in acetonitrile have been applied as test set for benchmarking computational methods for a series of compounds with only small structural differences. The aim of the study is to propose a simple method for calculating the standard oxidation potentials, and therefore, the protocol is progressively developed by adding more terms in the energy expression. In addition, the effect of including implicit solvation models (IEFPCM, CPCM, and SMD), larger basis sets, and correlation methods are investigated. The oxidation potentials calculated using the G3MP2B3 approach with IEFPCM resulted in the best fit (R2=0.9624), but the slope of the correlation line, 0.74, is far from the optimal value, 1.00. B3LYP/6-311++G(d,p) and TPSSh/6-311++G(2d,p) yielded only slightly less consistent data (R2=0.9388 and R2=0.9425), but with much better slopes, 1.00 and 0.94, respectively. We conclude that it is important to investigate the basis set size and treatment of electron correlation when calculating oxidation potentials for N,N,N',N' tetrasubstituted p-phenylenediamines.

AB - The formal potentials for the reversible one-electron oxidation of N,N,N',N' tetrasubstituted p-phenylenediamines in acetonitrile have been applied as test set for benchmarking computational methods for a series of compounds with only small structural differences. The aim of the study is to propose a simple method for calculating the standard oxidation potentials, and therefore, the protocol is progressively developed by adding more terms in the energy expression. In addition, the effect of including implicit solvation models (IEFPCM, CPCM, and SMD), larger basis sets, and correlation methods are investigated. The oxidation potentials calculated using the G3MP2B3 approach with IEFPCM resulted in the best fit (R2=0.9624), but the slope of the correlation line, 0.74, is far from the optimal value, 1.00. B3LYP/6-311++G(d,p) and TPSSh/6-311++G(2d,p) yielded only slightly less consistent data (R2=0.9388 and R2=0.9425), but with much better slopes, 1.00 and 0.94, respectively. We conclude that it is important to investigate the basis set size and treatment of electron correlation when calculating oxidation potentials for N,N,N',N' tetrasubstituted p-phenylenediamines.

U2 - 10.1039/D1CP02315B

DO - 10.1039/D1CP02315B

M3 - Journal article

VL - 23

SP - 20340

EP - 20351

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 36

ER -