On the large σ-hyperconjugation in alkanes and alkenes
作者： Judy I-Chia Wu , Changwei Wang , William Chadwick McKee , Paul von Ragué Schleyer , Wei Wu
DOI: 10.1007/S00894-014-2228-2
关键词: Localized molecular orbitals 、 Diamantane 、 Geminal 、 Computational chemistry 、 Alkane stereochemistry 、 Staggered conformation 、 Chemistry 、 Hyperconjugation 、 Conformational isomerism 、 Cyclobutadiene
摘要: The conventional view that the σ CC and σ CH bonds in alkanes and unsaturated hydrocarbons are so highly localized that their non-steric interactions are negligible is scrutinized by the block-localized wavefunction (BLW) method. Even molecules considered conventionally to be “strain free” and “unperturbed” have surprisingly large and quite significant total σ-BLW-delocalization energies (DEs) due to their geminal and vicinal hyperconjugative interactions. Thus, the computed BLW-DEs (in kcal mol− 1) for the …
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