Theoretical study on redox potentials of organic
radicals in different solvents
Received: 14 May 2010 / Accepted: 24 September 2010 / Published online: 25 November 2010
Ó Springer Science+Business Media B.V. 2010
Abstract The BMK density functional theory method has been used to examine
the redox potentials of organic radicals in different solvents (DMF, N,N-dimeth-
ylformamide; DMSO, dimethyl sulfoxide; MeCN, acetonitrile). The polarizable
continuum solvation model (PCM) was used to describe the solvation-free energies.
The one-electron electrochemical standard potentials (E
) of ca. 100 organic radi-
cals in three solvents were calculated using a single, uniﬁed theoretical method
whose reliability has been tested against almost all the available experimental data.
It was found that the mean absolute deviation (MAD) between the theory and
experiment was about 0.08 V. With the newly developed theoretical method in
hand, more redox potentials of organic radicals in these three solvents were pre-
dicted by this single, uniﬁed method. The results showed that the redox potentials of
organic radicals in different organic solvents including DMF and DMSO had good
correlations with their redox potentials in MeCN.
Keywords Density functional theory Á Redox potentials Á Organic radicals
The importance of radicals in chemical and biological reactions has been recognized
in recent years [1–4]. In order to facilitate the synthetic and mechanistic studies
involving radical intermediates, there is an imperative to know the redox potentials
of organic radicals in organic solvents, for redox potentials present the ability of the
Electronic supplementary material The online version of this article (doi:10.1007/s11164-010-0212-8)
contains supplementary material, which is available to authorized users.
H. Wang (&) Á C. Yu
Tianjin EconomicTechnological Development Area Polytechinc, Tianjin 300457, China
Res Chem Intermed (2010) 36:1003–1019