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Common Origin of Enthalpic and Entropic Substituent Effects in Reactions of Benzhydryl Cations with Nucleophiles
Author(s) -
Patz Matthias,
Mayr Herbert,
Bartl Jörg,
Steenken Steen
Publication year - 1995
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199504901
Subject(s) - substituent , nucleophile , chemistry , computational chemistry , medicinal chemistry , organic chemistry , catalysis
As long as an enthalpic barrier is present , a decrease in the electron‐releasing ability of X and Y causes an increase in the reaction rates of reaction (a) due to the lowering of the activation enthalpy, while the activation entropy remains constant. When the enthalpic barrier disappears, further decrease in the electron‐releasing ability of X and Y is associated with an increase in reactivity caused by an increase in the activation entropy.