Comment on “The Interplay between Steric and Electronic Effects in SN2 Reactions” |
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| Authors: | Willem‐Jan van Zeist F Matthias Bickelhaupt Prof Dr |
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| Institution: | Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Scheikundig Laboratorium der Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands), Fax: (+31)?20‐5987629 |
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| Abstract: | We respond to a paper by Fernández, Frenking, and Uggerud (FFU: Chem. Eur. J. 2009 , 15, 2166) in which they conclude that not steric hindrance but reduced electrostatic attraction and reduced orbital interactions are responsible for the SN2 barrier, in particular in the case of more highly substituted substrates, for example, F? + C(CH3)3F. We disagree with this conclusion, which we show is the result of neglecting geometry relaxation processes that are induced by increased Pauli repulsion in the sterically congested SN2 transition state. |
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| Keywords: | energy decomposition analysis molecular modeling nucleophilic substitution reaction mechanisms steric hindrance |
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