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The Coexistence of the Reactivity–Selectivity Principle and of Linear Free Energy Relationships: A Diffusion Clock for Determining Carbocation Reactivities
Author(s) -
Roth Michael,
Mayr Herbert
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.199522501
Subject(s) - carbocation , nucleophile , electrophile , reactivity (psychology) , chemistry , computational chemistry , diffusion , reaction rate constant , selectivity , competition (biology) , photochemistry , chemical physics , thermodynamics , organic chemistry , physics , quantum mechanics , kinetics , catalysis , medicine , alternative medicine , pathology , ecology , biology
Electrophilicity parameters of reactive carbocations and the rate constants of the reactions of such short‐lived species with uncharged nucleophiles can be determined simply by competition experiments [Eq. (a); R = Ar 1 Ar 2 CH]. The only prerequisite for this is that suitable pairs of nucleophiles must be chosen so that one of the parallel reactions is diffusion controlled.