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

The Journal of Physical Chemistry. a
István Szabó, Gábor Czakó

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...Continue Reading

References

May 29, 2003·Chemistry : a European Journal·Jason M GonzalesGyörgy Tarczay
Dec 18, 2007·The Journal of Chemical Physics·Thomas B AdlerHans-Joachim Werner
Aug 12, 2008·The Journal of Organic Chemistry·A Patrícia Bento, F Matthias Bickelhaupt
May 7, 2010·The Journal of Physical Chemistry. a·Jiaxu Zhang, William L Hase
Jan 20, 2015·Nature Communications·István Szabó, Gábor Czakó

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Citations

Feb 18, 2016·Chemistry : a European Journal·Jalal Z A LalooAbel de Cózar
Jan 23, 2016·The Journal of Physical Chemistry. a·Eduardo CarrascosaRoland Wester
Oct 17, 2015·The Journal of Physical Chemistry. a·Jiaxu ZhangWilliam Louis Hase
Aug 10, 2016·The Journal of Physical Chemistry Letters·Yan WangMinghui Yang
Nov 16, 2016·Physical Chemistry Chemical Physics : PCCP·Peng LiuYulong Xu
Jul 21, 2017·Physical Chemistry Chemical Physics : PCCP·Yong-Tao MaWilliam L Hase
Mar 16, 2018·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Trevor A HamlinF Matthias Bickelhaupt
Nov 11, 2017·Journal of Computational Chemistry·Ibon AlkortaPaul L A Popelier
Mar 29, 2019·Physical Chemistry Chemical Physics : PCCP·Domonkos A TasiGábor Czakó
Feb 6, 2020·Physical Chemistry Chemical Physics : PCCP·Domonkos A TasiGábor Czakó
Apr 7, 2020·Physical Chemistry Chemical Physics : PCCP·Lulu LiDong H Zhang
May 27, 2020·Physical Chemistry Chemical Physics : PCCP·Yan LiDunyou Wang
Apr 10, 2018·Chemical Science·Eduardo CarrascosaRoland Wester
Jul 12, 2017·The Journal of Physical Chemistry. a·István Szabó, Gábor Czakó
Oct 7, 2017·The Journal of Physical Chemistry. a·István Szabó, Gábor Czakó
Mar 25, 2017·The Journal of Physical Chemistry. a·Viktor Tajti, Gábor Czakó
Sep 20, 2018·The Journal of Physical Chemistry. a·Balázs Olasz, Gábor Czakó
Oct 12, 2021·Physical Chemistry Chemical Physics : PCCP·Chen LiDunyou Wang
Oct 29, 2021·The Journal of Physical Chemistry. a·Attila Á DékányGábor Czakó

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