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Studies on Radical Cations, III. The Type C Valence-Isomeric System Quadricyclane Radical Cation/Norbornadiene Radical Cation

✍ Scribed by Edwin Haselbach; Thomas Bally; Zuzana Lanyiova; Peter Baertschi

Publisher: John Wiley and Sons
Year: 1979
Tongue: German
Weight: 607 KB
Volume: 62
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.19790620226

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✦ Synopsis

Abstract

The previously discussed principles involved in electrocyclic reactions of openshell ions are exemplified for a type C system, the radical cation couple quadricyclane^+^ (Q^+^)/norbornadiene^+^ (NBD^+^). Exhaustive calculations (MINDO/3) for the various states of the ions support the general predictions for such types of systems. The barrier of interconversion Q^+^ → NBD^+^ is estimated to be significantly lower than that for the corresponding neutrals. Experimental support to this prediction is obtained by γ‐irradiation of Q or NBD in an electron scavenging matrix. In both cases only NBD^+^ is observed, indicating that Q^+^ is not stable at 77 K. Previous observations and propositions referring to the system Q^+^/NBD^+^ are discussed in view of the present findings.

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