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PE-spectroscopic investigation of nonconjugated π,π interactions in (seco)dodecahedradienes — on the route to an experimental ethylene/ethylene cycloaddition reaction coordinate

✍ Scribed by Martin, Hans-Dieter ;Mayer, Bernhard ;Weber, Klaus ;Wahl, Fabian ;Prinzbach, Horst


Publisher
John Wiley and Sons
Year
1995
Tongue
English
Weight
586 KB
Volume
1995
Category
Article
ISSN
0947-3440

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✦ Synopsis


Abstract

Nature and extent of nonconjugated π,π interactions in (bis)‐secododecahedradienes and (pentagonal, non‐pentagonal) dodecahedradienes with transannular π,π distances ranging from ca. 2.8 to ca. 3.5 Å – representing well defined points on the D~2h~ [π~2~ + π~2~] reaction coordinate – were studied by PE spectroscopy. The π,π splitting of 0.68 eV measured at the largest π,π distance of ca. 3.5 Å (1,16‐dodecahedradiene 3a) was attributed to ca. 50% each of through‐space and through‐bond conjugation (analysis of precanonical MOs).