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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Reversible Solution π-Dimerization and Long Multicenter Bonding in a Stable Phenoxyl Radical
Nico M Bonanno1, Prashanth K Poddutoori2, Kazunobu Sato3
1Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St.Catharines, Ontario, L2S3A1, Canada.
Abstract:
Reversible solution π-dimerization is observed in the stable neutral phenoxyl radical 2,6-bis-(8-quinolylamino)-4-(tert-butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π-extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π-dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.
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