SYNTHESES AND PHOTOELECTRON-SPECTRA OF 7-AZANORBORNADIENE AND RELATED-COMPOUNDS - AN ANALYSIS WITH FRAGMENT ORBITALS

被引:32
作者
ALTENBACH, HJ
CONSTANT, D
MARTIN, HD
MAYER, B
MULLER, M
VOGEL, E
机构
[1] UNIV DUSSELDORF,INST ORGAN CHEM & MAKROMOLEK CHEM,W-4000 DUSSELDORF 1,GERMANY
[2] UNIV COLOGNE,INST ORGAN CHEM,W-5000 COLOGNE 41,GERMANY
关键词
LONE-PAIR ORIENTATION; LONE PAIR INTERACTION; PRECANONICAL ORBITALS; ORBITALS; LOCALIZED; CALCULATIONS; ABINITIO STO-3G; MNDO; MM2 FORCE FIELD; PE SPECTROSCOPY;
D O I
10.1002/cber.19911240420
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The He(I) photoelectron spectra (PE) of 7-azanorbornane (5), 7-azanorbornene (6), and 7-azanorborandiene (7) as well as of related urethanes have been recorded. The syntheses of these bicyclic compounds are described in detail. A most convenient analysis of the PE spectroscopic results is based on the procedure of Heilbronner-Schmelzer on an ab initio STO-3G level. This method allows to construct fragment orbitals elucidating the orientation of the nitrogen lone pair, the through-space interaction with pi-bonds, and the participation of sigma-bond orbitals. The result is remarkable: whereas the direct interaction of localized lone-pair and pi-orbitals is significant in both syn- and anti-orientation, the interaction of a localized lone pair with a precanonical fragment pi-orbital is completely different in the two geometries. In 6-syn a considerable interaction matrix element F-psi,n-pi-syn = - 0.71 eV comes to the fore, whereas the corresponding parameter in 6-anti turns out to be almost zero, F-psi,n-pi-anti = + 0.09 eV. Since 6-syn is calculated to be more stable than 6-anti, it is this invertomer, 6-syn, which is likely to be responsible for the main bands in the PE spectrum of 6. The comparatively large experimental split between the first two PE bands of 6 (0.98 eV) is in accord with the 6-syn geometry and compares well with the calculated band separation of 1.26 eV for 6-syn.
引用
收藏
页码:791 / 801
页数:11
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