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A nonelectrocyclic path from the cyclobutene cation radical to the 1,3‐butadiene cation radical
Author(s) -
Bellville Dennis J.,
Chelsky Ronald,
Bauld Nathan L.
Publication year - 1982
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540030411
Subject(s) - cyclobutene , mindo , chemistry , radical ion , radical , ab initio , fragmentation (computing) , computational chemistry , ion , photochemistry , organic chemistry , molecule , ring (chemistry) , computer science , operating system
Abstract The conversion of the cyclobutene cation radical to the 1,3‐butadiene cation radical has been studied using MINDO /3 and ab initio SCF MO methods. Not only smooth electrocyclic but also stepwise, non‐electrocyclic routes were considered. Both calculational methods agree that the preferred reaction path is a novel nonelectrocyclic one proceeding through an intermediate “cyclopropylcarbinyl cation radical.” The quantitative agreement in the activation parameters calculated by the two methods is excellent. The proposed intermediate also provides an attractive explanation for the mass spectrometric fragmentation patterns of the cyclobutene and butadiene cation radicals.