The Interaction of π-Orbitals in Barrelene |
| |
Authors: | E Haselbach E Heilbronner G Schrder |
| |
Institution: | E. Haselbach,E. Heilbronner,G. Schröder |
| |
Abstract: | The photoelectron spectrum (PE. spectrum) of barrelene (bicyclo2.2.2]octatriene, 4 ) is recorded and the first four bands are correlated with orbitals obtained with the MINDO/2-SCF procedure. The structural changes accompagnying the ionisation process 4 → 4 + are qualitatively derived from the features of the top-occupied a′2 (π) MO of 4 , which shows complete σ-π separation. The vibrational pattern of the corresponding PE. band 1. as well as complete energy-minimisation of the geometries of 4 and 4 + support the conclusion that 4 is a rather strained molecule. The interaction of the three π? bonds in 4 are discussed in terms of ‘through-space’ and ‘through-bond’ interaction with lower lying σ-orbitals. It is found that the latter is far from being negligible. |
| |
Keywords: | |
|
|