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Nichtkonzertierte Cope‐Umlagerung? 1,2,6,7‐Cyclodecatetraen‐Thermolyse
Author(s) -
Roth Wolfgang R.,
Schaffers Thomas,
Heiber Margarita
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250330
Subject(s) - chemistry , diradical , cope rearrangement , thermal decomposition , concerted reaction , transition state , stereochemistry , activation energy , trapping , photochemistry , medicinal chemistry , catalysis , organic chemistry , ecology , physics , nuclear physics , singlet state , biology , excited state
Nonconcerted Cope‐Rearrangement? 1,2,6,7‐Cyclodecatetraene Thermolysis From the pressure and oxygen dependence of the trapping rate a two‐step mechanism for the Cope rearrangement of the title compound is deduced, its energy profile established, and the heat of formation of the intermediate diradical 3 determined. In contrast to the meso compound the rearrangement of the rac isomer proceeds by two competing processes, a concerted and a nonconcerted pathway. The different behavior of the meso and rac compound can be correlated to the boat and chair geometry of the respective transition states.