Double-inversion mechanisms of the X- + CH3Y [X,Y = F, Cl, Br, I] SN2 reactions

István Szabó, G. Czakó

Research output: Contribution to journalArticle

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Abstract

The double-inversion and front-side attack transition states as well as the proton-abstraction channels of the X- + CH3Y [X,Y = F, Cl, Br, I] reactions are characterized by the explicitly correlated CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory using small-core relativistic effective core potentials and the corresponding aug-cc-pVTZ-PP bases for Br and I. In the X = F case the double-inversion classical(adiabatic) barrier heights are 28.7(25.6), 15.8(13.4), 13.2(11.0), and 8.6(6.6) kcal mol-1 for Y = F, Cl, Br, and I, respectively, whereas the barrier heights are in the 40-90 kcal mol-1 range for the other 12 reactions. The abstraction channels are always above the double-inversion saddle points. For X = F, the front-side attack classical(adiabatic) barrier heights, 45.8(44.8), 31.0(30.3), 24.7(24.2), and 19.5(19.3) kcal mol-1 for Y = F, Cl, Br, and I, respectively, are higher than the corresponding double-inversion ones, whereas for the other systems the front-side attack saddle points are in the 35-70 kcal mol-1 range. The double-inversion transition states have XH···CH2Y- structures with Cs point-group symmetry, and the front-side attack saddle points have either Cs (X = F or X = Y) or C1 symmetry with XCY angles in the 78-88° range. On the basis of the previous reaction dynamics simulations and the minimum energy path computations along the inversion coordinate of selected XH···CH2Y- systems, we suggest that the double inversion may be a general mechanism for SN2 reactions.

Original languageEnglish
Pages (from-to)3134-3140
Number of pages7
JournalJournal of Physical Chemistry A
Volume119
Issue number12
DOIs
Publication statusPublished - Mar 26 2015

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Point groups
Crystal symmetry
Protons
inversions
Computer simulation
attack
saddle points
symmetry
protons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Double-inversion mechanisms of the X- + CH3Y [X,Y = F, Cl, Br, I] SN2 reactions. / Szabó, István; Czakó, G.

In: Journal of Physical Chemistry A, Vol. 119, No. 12, 26.03.2015, p. 3134-3140.

Research output: Contribution to journalArticle

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