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Elimination of the Barrier to Cope Rearrangement in Semibullvalene by Li + Complexation
Author(s) -
Jiao Haijun,
von Ragué Schleyer Paul
Publication year - 1993
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199317601
Subject(s) - ab initio , ion , activation barrier , cope rearrangement , chemistry , ab initio quantum chemistry methods , computational chemistry , transition state , crystallography , stereochemistry , density functional theory , molecule , organic chemistry , catalysis
The coordination of a Li + ion stabilizes the transition state for the Cope rearrangement of semibullvalene and essentially eliminates the barrier. At 0 K structure 1 is 0.7 kcal mol −1 lower in energy than the semibullvalene–Li + complex. Ab initio calculations also indicate that both species are homoaromatic.