‘Lone pair’ Electronic Structure, Conformation and Oxidation Behaviour of Diaziridines

Abstract

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 NHNH→NN 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.

The assignment of dissociative electron attachment bands in compounds containing hydroxyl and amino groups

“…Photoelectron spectra of various diamines, hydrazines and diazirines have been extensively studied because of the relation of the splitting of the n + and n − lone pair bands to the conformation of the compounds (twist angle along the N-N bond) and the competition of the 'through-space' and 'through-bond' interactions [40,41,42,43]. Tetramethylhydrazine has two amino groups linked together.…”

Chiral Recognition in Diaziridine Clusters and the Problem of Racemization Waves

“…Enantiomerically pure diaziridines, generally N,N‘-disubstituted, were described by Mannschreck and Seitz in 1967 − and have been the object of continuos interest (for a review and a recent paper see refs , ). In the solid state, the X-ray structure of only two N,N‘-unsubstituted diaziridines has been described with CSD 19 refcodes: OCIWUS and RAJQID.…”

“…9 The control and rationalization of these processes is of the utmost importance in the development of novel molecules designed as switches. 10 Enantiomerically pure diaziridines, generally N,N′-disubstituted, were described by Mannschreck and Seitz in 1967 [11][12][13][14][15][16] and have been the object of continuos interest (for a review and a recent paper see refs 17, 18). In the solid state, the X-ray structure of only two N,N′-unsubstituted diaziridines has been described with CSD 19 refcodes: OCIWUS and RAJQID.…”