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Ambident Reactivity of the Nitrite Ion Revisited
Author(s) -
Tishkov Alexander A.,
Schmidhammer Uli,
Roth Stefan,
Riedle Eberhard,
Mayr Herbert
Publication year - 2005
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200501274
Subject(s) - carbocation , reactivity (psychology) , chemistry , rationalization (economics) , medicinal chemistry , ion , computational chemistry , organic chemistry , philosophy , epistemology , medicine , alternative medicine , pathology
Lost control: The rationalization of the ambident reactivity of NO 2 − by the change between charge control to orbital control has to be revised. S N 1‐type reactions of carbocations with NO 2 − give kinetically controlled product mixtures only when these reactions proceed without activation energy (diffusion control). Activation‐controlled S N 1 alkylations are reversible and lead to the thermodynamically more stable nitro compounds.