Reaction mechanism conversion induced by the contest of nucleophile and leaving group

Abstract

Direct dynamic simulations have been employed to investigate OH− + CH3Cl reaction with the chosen B3LYP/aug-cc-pVDZ method. The calculated rate coefficient for bimolecular nucleophilic substitution reaction (SN2), 1.0 × 10-9...

Dynamics of nucleophilic substitution on ambident nucleophiles CN− and iodomethane: insights into the competition mechanism with neutral isomeric products

“…This reaction presents an obvious difference from the single nucleophile OH − + CH 3 Y S N 2 reaction, in which the trajectories are trapped in the post-reaction complex well. 45,46…”

“…This reaction presents an obvious difference from the single nucleophile OH À + CH 3 Y S N 2 reaction, in which the trajectories are trapped in the post-reaction complex well. 45,46 3.2.3 Product energies and velocity scattering angle. The total energy of the reaction includes the internal energy (vibration and rotation energies) of reactants CN À and CH 3 I, the initial collision energy, and the reaction enthalpy.…”

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

“…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. 31,32 Wang and co-workers performed QM/MM calculations for the OH − + CH 3 Y (Y = F, Cl and Br) S N 2 reactions in aqueous solution. [33][34][35] For the OH − + CH 3 I reaction, numerous experimental and theoretical investigations were carried out in the last decade.…”

“…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. 31,32 Wang and co-workers performed QM/MM calculations for the OH À + CH 3 Y (Y = F, Cl and Br) S N 2 reactions in aqueous solution.…”

“…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. 31,32 Wang and co-workers performed QM/MM calculations for the OH À + CH 3 Y (Y = F, Cl and Br) S N 2 reactions in aqueous solution. [33][34][35] For the OH À + CH 3 I reaction, numerous experimental and theoretical investigations were carried out in the last a Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Be ´la te ´r 1, Szeged H-6720, Hungary.…”