+ CH3Y [X = OH, SH, CN, NH2, PH2; Y = F, Cl, Br, I] SN2 Reactions

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Physical Chemistry Chemical Physics

Rethinking the X− + CH3Y [X = OH, SH, CN, NH2, PH2; Y = F, Cl, Br, I] SN2 reactions†

Domonkos A. Tasi, a Zita Fábiána and Gábor Czakó *a Author affiliations

* Corresponding authors

a Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720, Hungary E-mail: gczako@chem.u-szeged.hu

Abstract

Moving beyond the textbook mechanisms of bimolecular nucleophilic substitution (SN2) reactions, we characterize several novel stationary points and pathways for the reactions of X− [X = OH, SH, CN, NH2, PH2] nucleophiles with CH3Y [Y = F, Cl, Br, I] molecules using the high-level explicitly-correlated CCSD(T)-F12b method with the aug-cc-pVnZ(-PP) [n = D, T, Q] basis sets. Besides the not-always-existing traditional pre- and post-reaction ion-dipole complexes, X−⋯H3CY and XCH3⋯Y−, and the Walden-inversion transition state, [X–CH3–Y]−, we find hydrogen-bonded X−⋯HCH2Y (X = OH, CN, NH2; Y ≠ F) and front-side H3CY⋯X− (Y ≠ F) complexes in the entrance and hydrogen-bonded XH2CH⋯Y− (X = SH, CN, PH2) and H3CX⋯Y− (X = OH, SH, NH2) complexes in the exit channels depending on the nucleophile and leaving group as indicated in parentheses. Retention pathways via either a high-energy front-side attack barrier, XYCH3−, or a novel double-inversion transition state, XH⋯CH2Y−, having lower energy for X = OH, CN, and NH2 and becoming submerged (barrier-less) for X = OH and Y = I as well as X = NH2 and Y = Cl, Br, and I, are also investigated.

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Article information

DOI https://doi.org/10.1039/C8CP07850E Article type Paper Submitted 27 Dec 2018 Accepted 15 Mar 2019 First published 18 Mar 2019 This article is Open Access

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Phys. Chem. Chem. Phys., 2019,21, 7924-7931 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS

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Rethinking the X− + CH3Y [X = OH, SH, CN, NH2, PH2; Y = F, Cl, Br, I] SN2 reactions

D. A. Tasi, Z. Fábián and G. Czakó, Phys. Chem. Chem. Phys., 2019, 21, 7924 DOI: 10.1039/C8CP07850E

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