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A Guide to Tris(4-Substituted)-triphenylmethyl Radicals.

ABSTRACT: Triphenylmethyl (trityl, Ph₃C•) radicals have been considered the prototypical carbon-centered radical since their discovery in 1900. Tris(4-substituted)-trityls [(4-R-Ph)₃C•] have since been used in many ways due to their stability, persistence, and spectroscopic activity. Despite their widespread use, existing synthetic routes toward tris(4-substituted)-trityl radicals are not reproducible and often lead to impure materials. We report here robust syntheses of six electronically varied (4-RPh)₃C•, where R = NMe₂, OCH₃, ^tBu, Ph, Cl, and CF₃. The characterization reported for the radicals and related compounds includes five X-ray crystal structures, electrochemical potentials, and optical spectra. Each radical is best accessed using a stepwise approach from the trityl halide, (RPh)₃CCl or (RPh)₃CBr, by controllably removing the halide with subsequent 1e^- reduction of the trityl cation, (RPh)₃C⁺. These syntheses afford consistently crystalline trityl radicals of high purity for further studies.

SUBMITTER: Heuer AM

PROVIDER: S-EPMC10367072 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature

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A Guide to Tris(4-Substituted)-triphenylmethyl Radicals.

Heuer Abigail M AM Coste Scott C SC Singh Gurjot G Mercado Brandon Q BQ Mayer James M JM

The Journal of organic chemistry 20230705 14

Triphenylmethyl (trityl, Ph<sub>3</sub>C•) radicals have been considered the prototypical carbon-centered radical since their discovery in 1900. Tris(4-substituted)-trityls [(4-R-Ph)<sub>3</sub>C•] have since been used in many ways due to their stability, persistence, and spectroscopic activity. Despite their widespread use, existing synthetic routes toward tris(4-substituted)-trityl radicals are not reproducible and often lead to impure materials. We report here robust syntheses of six electron ...[more]

PMID: 37403939

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Project description:The azide radical (N3●) is one of the most important one-electron oxidants used extensively in radiation chemistry studies involving molecules of biological significance. Generally, it was assumed that N3● reacts in aqueous solutions only by electron transfer. However, there were several reports indicating the possibility of N3● addition in aqueous solutions to organic compounds containing double bonds. The main purpose of this study was to find an experimental approach that allows a clear assignment of the nature of obtained products either to its one-electron oxidation or its addition products. Radiolysis of water provides a convenient source of one-electron oxidizing radicals characterized by a very broad range of reduction potentials. Two inorganic radicals (SO4●-, CO3●-) and Tl2+ ions with the reduction potentials higher, and one radical (SCN)2●- with the reduction potential slightly lower than the reduction potential of N3● were selected as dominant electron-acceptors. Transient absorption spectra formed in their reactions with a series of quinoxalin-2-one derivatives were confronted with absorption spectra formed from reactions of N3● with the same series of compounds. Cases, in which the absorption spectra formed in reactions involving N3● differ from the absorption spectra formed in the reactions involving other one-electron oxidants, strongly indicate that N3● is involved in the other reaction channel such as addition to double bonds. Moreover, it was shown that high-rate constants of reactions of N3● with quinoxalin-2-ones do not ultimately prove that they are electron transfer reactions. The optimized structures of the radical cations (7-R-3-MeQ)●+, radicals (7-R-3-MeQ)● and N3● adducts at the C2 carbon atom in pyrazine moiety and their absorption spectra are reasonably well reproduced by density functional theory quantum mechanics calculations employing the ωB97XD functional combined with the Dunning's aug-cc-pVTZ correlation-consistent polarized basis sets augmented with diffuse functions.

Dataset Information

A Guide to Tris(4-Substituted)-triphenylmethyl Radicals.

Publications

A Guide to Tris(4-Substituted)-triphenylmethyl Radicals.

Similar Datasets

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