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Title: (Iso)pagodane radical cations in liquid hydrocarbons: `Time-resolved fluorescence-detected magnetic resonance` study of valence isomeric radical cations

Abstract

The `tight` (T), cyclobutanoid, and the `extended` (E), {pi}-complex-like, four-centred-three-electron radical cations (4c/3e) derived from (iso)pagodanes and from the valence isomeric (iso)dienes can be viewed as well-separated stationary points on the reaction coordinate for the ethylene/ethylene radical cation [2+1]cycloaddition. So far, experimentally verified examples (ESR, CV, PE) are the extended [1.1.1.1](2{sup .+}) and iso-[2.2.1.1](4{sup .+})ions, persistent in fluid solution at room temperature, and the tight iso-[1.1.1.1]{sup .+} and [2.2.1.1]{sup .+} ions, observable only in Freon matrix (CFCl{sub 3}, {gamma}-rays, 77K). According to calculations, these are the thermodynamically more stable ones of the respective pairs of valence isomers. In this communication the direct observation of tight 1{sup .+} and the activation barrier for its isomerization into extended 2{sup .+} are reported. 16 refs., 3 figs., 1 tab.

Authors:
;  [1]; ;  [2]; ;  [3]
  1. Argonne National Lab., IL (United States)
  2. TU Braunschweig (Germany)
  3. Universitaet Freiburg (Germany)
Publication Date:
OSTI Identifier:
405323
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 118; Journal Issue: 39; Other Information: PBD: 2 Oct 1996
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; CATIONS; FLUORESCENCE; MAGNETIC RESONANCE; SPECTRA; ALKANES; RADICALS; HYDROCARBONS; ISOMERS; CALCULATION METHODS

Citation Formats

Trifunac, A D, Werst, D W, Herges, R, Neumann, H, Prinzbach, H, and Etzkorn, M. (Iso)pagodane radical cations in liquid hydrocarbons: `Time-resolved fluorescence-detected magnetic resonance` study of valence isomeric radical cations. United States: N. p., 1996. Web. doi:10.1021/ja961035v.
Trifunac, A D, Werst, D W, Herges, R, Neumann, H, Prinzbach, H, & Etzkorn, M. (Iso)pagodane radical cations in liquid hydrocarbons: `Time-resolved fluorescence-detected magnetic resonance` study of valence isomeric radical cations. United States. https://doi.org/10.1021/ja961035v
Trifunac, A D, Werst, D W, Herges, R, Neumann, H, Prinzbach, H, and Etzkorn, M. 1996. "(Iso)pagodane radical cations in liquid hydrocarbons: `Time-resolved fluorescence-detected magnetic resonance` study of valence isomeric radical cations". United States. https://doi.org/10.1021/ja961035v.
@article{osti_405323,
title = {(Iso)pagodane radical cations in liquid hydrocarbons: `Time-resolved fluorescence-detected magnetic resonance` study of valence isomeric radical cations},
author = {Trifunac, A D and Werst, D W and Herges, R and Neumann, H and Prinzbach, H and Etzkorn, M},
abstractNote = {The `tight` (T), cyclobutanoid, and the `extended` (E), {pi}-complex-like, four-centred-three-electron radical cations (4c/3e) derived from (iso)pagodanes and from the valence isomeric (iso)dienes can be viewed as well-separated stationary points on the reaction coordinate for the ethylene/ethylene radical cation [2+1]cycloaddition. So far, experimentally verified examples (ESR, CV, PE) are the extended [1.1.1.1](2{sup .+}) and iso-[2.2.1.1](4{sup .+})ions, persistent in fluid solution at room temperature, and the tight iso-[1.1.1.1]{sup .+} and [2.2.1.1]{sup .+} ions, observable only in Freon matrix (CFCl{sub 3}, {gamma}-rays, 77K). According to calculations, these are the thermodynamically more stable ones of the respective pairs of valence isomers. In this communication the direct observation of tight 1{sup .+} and the activation barrier for its isomerization into extended 2{sup .+} are reported. 16 refs., 3 figs., 1 tab.},
doi = {10.1021/ja961035v},
url = {https://www.osti.gov/biblio/405323}, journal = {Journal of the American Chemical Society},
number = 39,
volume = 118,
place = {United States},
year = {Wed Oct 02 00:00:00 EDT 1996},
month = {Wed Oct 02 00:00:00 EDT 1996}
}