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Isotope Effects in the Solvolysis of Sterically Hindered Arenesulfonyl Chlorides
Author(s) -
Iazykov Mykyta,
Canle L. Moisés,
Santaballa J. Arturo,
Rublova Ludmila
Publication year - 2015
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20945
Subject(s) - chemistry , solvolysis , kinetic isotope effect , steric effects , solvent , molecule , photochemistry , alkyl , transition state , solvent effects , computational chemistry , organic chemistry , hydrolysis , deuterium , catalysis , physics , quantum mechanics
ABSTRACT Solvent isotope effects in the ethanolysis of sterically hindered arenesulfonyl chlorides ruled out a proton transfer in the rate‐determining step and agreed with a S N 2 mechanism involving at least a second solvent molecule in the transition state (TS). The lack of a secondary kinetic isotope effect in the o ‐alkyl groups allows us to disregard the possible contribution of σ–π hyperconjugation. The measured activation parameters are consistent with a S N 2 mechanism involving the participation of solvent molecules in the TS, possibly forming a cyclic TS through a chain of solvent molecules.