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

J Org Chem. 2023 Jul 21;88(14):9893-9901. doi: 10.1021/acs.joc.3c00658. Epub 2023 Jul 5.

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.