Chemical reactions inside structured nano-environment: SN2vs. E2 reactions for the F− + CH3CH2Cl system

Literature Information

Publication Date 2010-10-29
DOI 10.1039/C0CP01182G
Impact Factor 3.676
Authors

Josefredo R. Pliego Jr.


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Abstract

A new receptor for SN2 transition states, named NPTROL, is proposed. This molecule has a cavity and four hydroxyl groups that are able to interact with ionic SN2 and E2 transition states. Its catalytic effect and selectivity was investigated through high level ab initio calculations using the fluoride ion plus ethyl chloride in DMSO solution as a model system. Calculations at the ONIOM[CCSD(T)/6-311+G(2df,2p) : MP2/BASIS1] level of theory and solvent effects, included through a continuum solvation model, indicate that NPTROL is able to catalyze the SN2 pathway and has an inverse effect on the E2 pathway. Inside the NPTROL cavity, the ΔG‡ for the SN2 transition state is 5.00 kcal mol−1 lower than that for E2, and as a consequence this reaction becomes highly selective toward the SN2 product.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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