Isotope Effects in the Solvolysis of Sterically Hindered Arenesulfonyl Chlorides |
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| Authors: | Mykyta Iazykov Moisés Canle L J Arturo Santaballa Ludmila Rublova |
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| Affiliation: | 1. Department of General Chemistry, Faculty of Ecology and Chemical Technology, Donetsk National Technical University, Donetsk, Ukraine;2. Chemical Reactivity and Photoreactivity Group, Departamento de Química Física e Enxe?aría Química, Faculty of Sciences and Center for Advanced Scientific Research (CICA), University of A Coru?a, Coru?a, Spain |
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| 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 SN2 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 SN2 mechanism involving the participation of solvent molecules in the TS, possibly forming a cyclic TS through a chain of solvent molecules. |
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