Why is there no in-plane H-atom transfer from aryloxy radicals? A theoretical and experimental investigation.
A combined experimental and theoretical study of the mechanisms and energies associated with intramolecular H-atom transfers from methyl groups with varying numbers of phenyl substituents to oxygen atoms of aryloxy radicals is reported. It is shown that the transfers within the six aryloxy radicals investigated would have high activation energies and, in all but one case, are endothermic. A detailed analysis of the calculated reaction coordinates indicates proton-coupled electron transfers as the favored mechanisms.
Chen
Yu-Zhe
YZ
Department of Chemistry, Georgetown University, Washington, DC 20057-1227, USA.
Tian
Yong-Hui
YH
Kertesz
Miklos
M
Weiss
Richard G
RG
D004579:Electron Transport; D005609:Free Radicals / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D008962:Models, Theoretical; D011522:Protons; D011789:Quantum Theory
D005609:Free Radicals; D011522:Protons; D006859:Hydrogen