The Preorganization Step in Organic Reaction Mechanisms. Charge-Transfer Complexes as Precursors to Electrophilic Aromatic Substitutions

Metastable (pre-reactive) intermediates, as commonplace transients in simple bimolecular reactions, are usually unobserved (and ignored)−though they provide vital mechanistic insight. Thus, the preequilibrium (charge-transfer) complexes of various aromatic donors with rather typical electron accepto...

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Bibliographic Details
Published in:Journal of organic chemistry 2002-03, Vol.67 (6), p.1727-1737
Main Authors: Rosokha, Sergiy V, Kochi, Jay K
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
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Summary:Metastable (pre-reactive) intermediates, as commonplace transients in simple bimolecular reactions, are usually unobserved (and ignored)−though they provide vital mechanistic insight. Thus, the preequilibrium (charge-transfer) complexes of various aromatic donors with rather typical electron acceptors such as Br2, NO+, and NO2 + are examined quantitatively (via their molecular and electronic structures) to reveal surprisingly unorthodox aspects of what is conventionally referred to in organic chemistry textbooks as electrophilic aromatic bromination, nitrosation, and nitration, respectively.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo011072r