This paper re-examines gas-phase S(N)2 reactions at saturated carbon for model reactions Nu(-) + CH(3)Cl --> CH(3)Nu + Cl(-) (Nu(-) = HO(-), MeO(-), NH(2)(-), HS(-), Cl(-), Br(-), I(-), HOO(-), MeOO(-), HSS(-), and NH(2)NH(-)) using the G2(+) theory. The calculated results show that the alpha-effect does exist in the gas-phase S(N)2 reaction at the sp(3) carbon, contrary to the currently accepted notion of the absence of the alpha-effect in the gas phase.
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http://dx.doi.org/10.1021/ol0526930 | DOI Listing |
ACS Phys Chem Au
November 2024
Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.
Roundabout (RA) is an important indirect mechanism for gas-phase X + CHY → XCH + Y S2 reactions at a high collision energy. It refers to the rotation of the CH-group by half or multiple circles upon the collision of incoming nucleophiles before substitution takes place. The RA mechanism was first discovered in the Cl + CHI S2 reaction to explain the energy transfer observed in crossed molecular beam imaging experiments in 2008.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
MTA-SZTE Lendület "Momentum" Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Szeged H-6720, Hungary.
J Chem Phys
November 2024
MTA-SZTE Lendület "Momentum" Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720, Hungary.
Precis Chem
January 2024
State Key Laboratory of Urban Water Resource and Environment, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, P. R. China.
The prototypical E2 elimination and S2 substitution reactions between microsolvated fluoride and ethyl bromide show unexpected dynamic behaviors in mechanistic evolution driven by solvation and collision activation. Considering the steric effects, the gas-phase selectivity favors an E2 pathway barely dependent on collision energies. Remarkably, base solvation steers the reaction in an effective way toward substitution at a near-thermal energy, whereas the governing high-energy events retain elimination.
View Article and Find Full Text PDFJ Phys Chem B
October 2024
Institute for Systems and Physical Biology, Shenzhen Bay Laboratory, Shenzhen 518055, China.
We present a tutorial to carry out umbrella-sampling free-energy simulations with a combined quantum mechanical and molecular mechanical (QM/MM) potential, which may also be used in a computational or biophysical chemistry curriculum for first-year graduate and undergraduate students. In this article, we choose the Type II S2 Menshutkin reaction between ammonia and chloromethane to construct the potential of mean force (PMF) for the reaction in aqueous solution. In this exercise, we wish to accomplish three tasks: (1) an understanding of the concept of PMF and the umbrella-sampling free-energy simulation method, (2) the use of a combined QM/MM potential in molecular dynamics simulation of chemical reactions, and (3) an understanding of solvent effects and intermolecular interactions on chemical reactions through comparison with gas-phase results.
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