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The effect of substituting phosphorus for a ring carbon atom in the valence isomers cyclobutene, bicyclobutane, and 1,3‐butadiene. a quantum‐chemical investigation
Author(s) -
Schoeller Wolfgang W.,
Tubbesing Ulrike
Publication year - 1996
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.19961290410
Subject(s) - cyclobutene , chemistry , valence (chemistry) , ab initio , computational chemistry , quantum chemical , ab initio quantum chemistry methods , ring (chemistry) , photochemistry , molecule , organic chemistry
Cyclobutene, bicyclobutane, and 1,3‐butadiene are valence isomers within the concept of the Woodward‐Hoffman rules. According to thermochemical considerations and in agreement with energy optimized quantum‐chemical calculations at the ab initio RHF and MP2/6‐31G(d,p) levels bicyclobutane is the least and 1,3‐butadiene the most stable valence isomer. Phosphorus substitution exerts a considerable effect on the relative stabilities of the various valence isomers. Bicyclobutanes containing phosphorus atoms in the bridgehead positions are considerably more stable than the other phosphorus‐substituted valence isomers. This conclusion was confirmed by an analysis of the natural bond populations.