PHOTOELECTRON-SPECTRA OF ALKYLDIAZIRIDINES

KLASINC, L and MANNSCHRECK, A and MINTAS, M and MCGLYNN, SP (1994) PHOTOELECTRON-SPECTRA OF ALKYLDIAZIRIDINES. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 (9). pp. 2059-2062. ISSN 0300-9580,

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Abstract

Hel photoelectron (PES) spectra have been obtained for six trisubstituted and three tetrasubstituted diaziridines: 1,3,3-trimethyldiaziridine (1), 1-isopropyl-3,3-dimethyldiaziridine (2), 1-methylspiro-[diaziridine-3,1 -cyclopentane] (3), 1-benzyl-3,3-dimethyldiaziridine (4). 3-benzyl-1,3-dimethyldiaziridine (5), 3,3-dibenzyl-1-methyldiaziridine (6), tetramethyldiaziridine (7 or Me-1), 1-benzyl-2,3,3-trimethyldiaziridine (8 or Me-4) and 3-benzyl-1,2,3-trimethyldiaziridine (9 or Me-5). Analysis provided information about the outer valence electronic structures and geometric conformations. The observed splitting of the n(+) and n(-) ionization events indicates that all compounds exist in trans configurations; the lone pair-lone pair dihedral angle is 100 less than or equal to theta/deg less than or equal to 110; and theta decreases with substitution. The centre of gravity of the two lone-pair ionizations remains fairly constant at E=9.5(9.15) eV for trialkyl (tetraalkyl) substitution. N-Alkylation has a much greater effect on the electronic structure of diaziridine than does C-alkylation. The additional phenyl group of benzyl substituents and the p-methoxyphenyl group of 1-(p-methoxybenzyl)-3,3-dimethyldiaziridine (10) exert negligible influences. The 1,3-trisubstituted diaziridine 10 decomposes thermally to form NH3, a reaction described previously only for 3,3-dialkyl- and 1,2.3-trialkyl-diaziridines.

Item Type: Article
Uncontrolled Keywords: ENANTIOMERIC DIAZIRIDINES; PREPARATIVE SEPARATIONS; ELECTRONIC-STRUCTURE; TETRAALKYLHYDRAZINES; RACEMIZATIONS; SPECTROSCOPY; HYDRAZINES;
Depositing User: Dr. Gernot Deinzer
Last Modified: 19 Oct 2022 08:39
URI: https://pred.uni-regensburg.de/id/eprint/53119

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