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Small and Medium Rings, 771) Nonconjugated π,π Interactions Approaching Classical π,π Conjugation – PE-Spectroscopical Investigation of the 7,8;12,19-Diseco-1,16-dodecahedradiene System

✍ Scribed by Elsässer, Dominik ;Hassenrück, Karin ;Martin, Hans-Dieter ;Mayer, Bernhard ;Lutz, Georg ;Prinzbach, Horst


Publisher
Wiley (John Wiley & Sons)
Year
1991
Tongue
English
Weight
631 KB
Volume
124
Category
Article
ISSN
0009-2940

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✦ Synopsis


Disecododecahedradienes / Pagodanes / PE spectroscopy / x-Orbital interaction / Orbitals, localized, precanonical / Orbital interaction, through-space Transannular [orbital) interactions in compounds 1 -9 are studied by means of He(I,)-PE spectroscopy. Unusually strong through-space-dominated n,x interaction is found to be operative in the nonconjugated 1,B-dienes 1, 2, 7, and 8. The n,n splitting of 1.9 eV for disecododecahedradiene 1 is even sur-passed by the record value of 2.2 eV for disecodienedione 2, which almost equals that in 1,3-butadiene (2.46 eV). The experimental results are explained by computational methods, especially by analyses of the precanonical MOs.

3

Distances in pm.