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Chemical Reactivity Controlled by Negative Hyperconjugation: A Theoretical Study
Author(s) -
Nilsson Lill Sten O.,
Rauhut Guntram,
Anders Ernst
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200304878
Subject(s) - hyperconjugation , chemistry , reactivity (psychology) , computational chemistry , nucleophile , density functional theory , transition state , stereochemistry , molecule , organic chemistry , catalysis , medicine , alternative medicine , pathology
Negative hyperconjugation is a general phenomenon that can be observed in many areas of chemistry. The knowledge of its impact on structural parameters and conformational issues is well established, but little is known about its importance for chemical reactivity. Here we present a systematic study of different aspects of negative hyperconjugation on the reactivity of complex heterocyclic systems using density functional theory. Intermediates from the reaction of nitrogen‐based nucleophiles with bis(1,3,4‐thiadiazolo)‐1,3,5‐triazinium halides serve as benchmark systems to demonstrate the effects of negative hyperconjugation on bond lengths, on the relative stability of conformational isomers and transition structures and, most importantly, on the different reaction pathways of these species. The computational results provided here are in part supported by experiments reported elsewhere.