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‘Lone pair’ Electronic Structure, Conformation and Oxidation Behaviour of Diaziridines
Author(s) -
Haselbach Edwin,
Mannschreck Albrecht,
Seitz Werner
Publication year - 1973
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19730560517
Subject(s) - chemistry , lone pair , ionization , computational chemistry , ionization energy , electronic structure , electron pair , alkyl , electron , stereochemistry , molecule , organic chemistry , quantum mechanics , ion , physics
Photoelectron spectroscopic investigations indicate that (i) monocyclic diaziridines prefer a trans ‐conformation of the nitrogen‐lone pairs, and (ii) the interaction between these is comparable to that exhibited by open‐chain analogues, i.e . alkyl‐substituted hydrazines. The chemical experience concerning the particular case of NHNH→NN oxidation of diaziridines can therefore not be accounted for by a prevailing unfavorable ‘lone pair’ interaction. Thermochemical as well as entropy arguments may serve as an explanation. A rather unsatisfactory agreement between predictions from various theoretical procedures and experimental results for the ionization potentials of ‘lone pair’ MO electrons is noted.