Studies on Radical Cations, III. The Type C Valence-Isomeric System Quadricyclane Radical Cation/Norbornadiene Radical Cation
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...
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Veröffentlicht in: | Helvetica chimica acta 1979-03, Vol.62 (2), p.583-592 |
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Hauptverfasser: | , , , |
Format: | Artikel |
Sprache: | eng |
Online-Zugang: | Volltext |
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Zusammenfassung: | 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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ISSN: | 0018-019X 1522-2675 |
DOI: | 10.1002/hlca.19790620226 |