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Updated: Jun 17, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Rearrangement of Dewar benzene derivatives studied by DFT
Martin Dracínský1, Obis Castaño, Martin Kotora
1Institute of Organic Chemistry and Biochemistry, Academy of Sciences, 166 10 Prague, Czech Republic. dracinsky@uochb.cas.cz
Abstract:
Skeletal rearrangement of a series of substituted Dewar benzenes to biaryl products was studied with DFT methods. Excellent agreement of calculated free energies of activation with experimental kinetic data was achieved. Two different transition states were proposed to be involved in the rearrangement. The reaction path was studied both by static intrinsic reaction coordinate (IRC) calculations and first-principles Car-Parrinello and Born-Oppenheimer molecular dynamics. All approaches confirmed the suggested reaction mechanism.
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