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Electron‐Transfer‐Catalyzed cis → trans Isomerization of 1,1′‐Azonorborane . Prototype of a reversible two‐stage storage system
Author(s) -
Gescheidt Georg,
Lamprecht Axel,
Heinze Jürgen,
Schuler Barbara,
Schmittel Michael,
Kiau Susanne,
Rüchardt Christoph
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.19920750515
Subject(s) - isomerization , chemistry , radical ion , catalysis , electron transfer , cyclic voltammetry , photochemistry , ion , medicinal chemistry , electrochemistry , organic chemistry , electrode
ESR and cyclic voltammetry investigations show that isomerization of the radical cation of cis ‐1,1′‐azonorbornane ( cis ‐ 1 ) to the trans ‐radical ion proceeds too fast in solution for direct investigation of the cis ‐radical ion even at −78°. The facile isomerization of the radical cation is in agreement with PM 3 calculations proposing an activation barrier of only 17 kJ/mol. As a consequence, quantitative cis → trans isomerization of 1,1′‐azonorbornane can effectively be accomplished by addition of catalytic amounts of one‐electron oxidants. This is the first evidence for a radical‐cation‐catalyzed cis → trans isomerization of azo compounds.