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Radical Cations and Radical Anions of Three Bridgehead Azopolycycloalkanes: A fluid‐solution ESR study
Author(s) -
Gescheidt Georg,
Lamprecht Axel,
Rüchardt Christoph,
Schmittel Michael
Publication year - 1992
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.19920750131
Subject(s) - chemistry , radical , octane , alkane , radical ion , free radical addition , spectroscopy , ion , photochemistry , hydrocarbon , organic chemistry , physics , quantum mechanics
Abstract The radical mono‐ions of three azoalkanes in which the azo group is connected to the polycyclic alkane moieties at the bridgehead C‐atoms, i.e. 1,1′‐azonorbornane ( 1 ), 1,1′‐azotwistane ( 2 ), and 1,1′‐azobicyclo[3.2.1]octane ( 3 ), were studied in fluid solution by ESR spectroscopy. According to the ESR parameters and MO models, the radical cations of 1–3 should be considered as σ radicals, whereas the corresponding radical anions are π radicals. INDO calculations point to a a remarkable dependence of the 14 N‐coupling constants on the geometry at the N‐atoms in the radical cations of aliphatic azo compounds.