Proton transfer-induced competing product channels of microsolvated Y⁻(H₂O)_n + CH₃I (Y = F, Cl, Br, I) reactions

Abstract

The potential energy profiles of three proton transfer involved product channels for the reactions of Y−(H2O)1,2 + CH3I (Y = F, Cl, Br, I) were characterized with B97-1/ECP/d method. These...

Quasi-classical trajectory study of the OH− + CH3I reaction: theory meets experiment

“…In the post-reaction CH 3 OH•••F − complex the leaving F − may remove the proton of the hydroxyl group, which leads to the products of HF + CH 3 O − . 25,26 The existence of the oxide ion substitution for OH − + CH 3 F was also confirmed by Li and co-workers, 27 28 The OH − + CH 3 Cl S N 2 reaction were examined by various studies, as well. The stationary points were identified by Evanseck et.…”

“…25,26 The existence of the oxide ion substitution for OH À + CH 3 F was also confirmed by Li and coworkers, 27 and Ji et al completed a detailed mapping of the possible proton abstraction-involved channels for the Y À (H 2 O) n + CH 3 I (Y = F, Cl, Br, I) reactions, where n = 1 or 2, taking into account an oxide ion substitution leading to the CH 3 O À + HY + HI + (n À 1)H 2 O products. 28 The OH À + CH 3 Cl S N 2 reaction was examined by various studies as well. The stationary points were identified by Evanseck et al, 10 and later the results were recalculated by Tachikawa et al, 11 Souza et al, 29 Laloo et al 30 and Zhao et al 31 using DFT, HF, MP2 and CCSD(T) methods; moreover, direct dynamics simulations were also conducted at the HF/3-21+G(d) and B3LYP/aug-cc-pVDZ levels of theory.…”

Deciphering the Microdroplet Acceleration Factors of Aza-Michael Addition Reactions

“…Partial solvation has been proposed to be responsible for the rate acceleration in several organic reactions, including substitution, redox, addition, and elimination reactions. ,− Solvent molecules not only affect the reactivity by the solute–solvent interaction but also catalyze the reactions or alter the mechanism/products. ,, To investigate the potential catalytic role of solvent molecules, we constructed microsolvated systems by introducing one to three explicit methanol solvent molecules to the system. Because the air–water interface can be regarded as a transition from the microsolvated phase to the bulk liquid phase, the comparison between the microsolvated system and liquid phase helps to estimate the barrier at the air–water interface.…”

Competitive dynamics of E2 and SN2 reaction driven by collision energy and leaving group

“…On the other hand, a good leaving group is defined by the extent to which it lowers the transition-state barrier of the reaction. 15,16 The ability of a substituent Y to be a good leaving group is usually related to its basicity or electronegativity, i.e. , its capacity to receive additional negative charges, and the strength of the C–Y bond.…”

“…8 On the other hand, a good leaving group is defined by the extent to which it lowers the transition-state barrier of the reaction. 15,16 The ability of a substituent Y to be a good leaving group is usually related to its basicity or electronegativity, i.e., its capacity to receive additional negative charges, and the strength of the C-Y bond. 17,18 Recently, a reactive scattering experiment has been developed for the direct imaging of the differential cross sections (DCSs) of F À + (CH 3 ) 3 CY (Y = Cl, I) reactions.…”