Double-Inversion Mechanisms of the X- + CH3Y [X,Y = F, Cl, Br, I] SN2 Reactions

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 center dot center dot center dot 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 degrees range. On the basis of the previous reaction dynamics simulations and the minimum energy path computations along the inversion coordinate of selected XH center dot center dot center dot CH2Y- systems, we suggest that the double inversion may be a general mechanism for SN2 reactions.