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• W2078184472 abstract "The gas-phase acyl transfer reactions X- + RCOY ↔ RCOX + Y- with R = H, CH3 and X, Y = Cl, Br have been investigated with MO theory at the G2(+)MP2 level. Attempts have been made to locate two types of adducts, a tetrahedral adduct formed by an out-of-plane π-attack (π-adduct) and an adduct formed by an in-plane σ-attack (σ-adduct). In all cases, the σ-type adducts are nonexistent. Careful examination of the energies (ΔE) at the MP2/6-311+G** level shows that the transition structure region is very flat with a very low barrier for decomposition of the intermediate. This small barrier becomes inverted (i.e., the intermediate level is higher than the transition state) as the zero-point and thermal energy corrections are applied, which is eventually restored to the normal barrier (δΔG = ΔGTS − ΔGInt ≅ −0.9 kcal mol-1) when entropy effect is accounted for. The π-adducts are stabilized mainly by the proximate second-order σ-σ* type charge transfer interactions. The solvent effect evaluated in acetonitrile by the IPCM (isodensity polarizable continuum model) method raises activation energies, ΔG≠, by 9 ∼ 13 kcal mol-1, but the relative reactivity order in the gas phase, −ΔG≠(X,Y):(Cl, Br) > (Cl, Cl) > (Br, Br) > (Br, Cl), is maintained in solution. The stepwise mechanism predicted in the gas phase and in solution is consistent with the experimental result." @default.
• W2078184472 created "2016-06-24" @default.
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• W2078184472 date "2000-04-07" @default.
• W2078184472 modified "2023-09-30" @default.
• W2078184472 title "Ab Initio Study of the X^- + RCOY Displacement Reactions with R = H, CH₃ and X, Y = Cl, Br" @default.
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• W2078184472 doi "https://doi.org/10.1021/jp994238p" @default.
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