ArticleJournal of the American Chemical Society2020
Solvation Dynamics and the Nature of Reaction Barriers and Ion-Pair Intermediates in Carbocation Reactions.
Article in Journal of the American Chemical Society, 2020. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 16 papers.
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Who cites it
16 citing papers in PubMed.
- Nuclear Quantum Effects on the Organic Bifurcation Reaction in Microsolvated Water Clusters: Ring-Polymer Molecular Dynamics Calculations Using an Explicit Solvation Model.Journal of computational chemistry · 2026Article
- A Bifunctional Aminoxyl-Bipyridine Peptide Catalyst for the Atroposelective Copper-Catalyzed Aerobic Oxidation of Biaryl Diols.Journal of the American Chemical Society · 2026Article
- Solvent-temperature coupled hydride transfer controls product selectivity in the HSiRChemical science · 2026Article
- Ab Initio Molecular Dynamics Simulations for Organic Chemists─It is About Time!Journal of the American Chemical Society · 2026Review
- Solvent Effects on the Selectivity of Ambimodal Dipolar/Diels-Alder Cycloadditions: A Study Using Explicit Solvation Models.Chemphyschem : a European journal of chemical physics and physical chemistry · 2025Article
- Predicting Selectivity with a Bifurcating Surface: Inaccurate Model or Inaccurate Statistics of Dynamics?The journal of physical chemistry. A · 2024Article
- Analogies between photochemical reactions and ground-state post-transition-state bifurcations shed light on dynamical origins of selectivity.Nature chemistry · 2024Article
- Interfacial Electrochemical Lithiation and Dissolution Mechanisms at a Sulfurized Polyacrylonitrile Cathode Surface.ACS energy letters · 2024Article
- Advancements in hydrochlorination of alkenes.Beilstein journal of organic chemistry · 2024Review
- Accelerating explicit solvent models of heterogeneous catalysts with machine learning interatomic potentials.Chemical science · 2023Article
- Reaction dynamics studiedChemical science · 2022Review
- Controllable preparation and performance of bio-based poly(lactic acid-iminodiacetic acid) as sustained-release PbiScience · 2021Article
- A dynamic picture of the halolactonization reaction through a combination ofChemical science · 2021Article
- The Chemistry of Short-Lived α-Fluorocarbocations.The Journal of organic chemistry · 2021Article
- Kinetic effects of molecular clustering and solvation by extended networks in zeolite acid catalysis.Chemical science · 2021Review
- Ab Initio Molecular Dynamics Simulations of the SJournal of the American Chemical Society · 2021Article
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2 authors.
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Abstract
Additions of acids to 1,3-dienes are conventionally understood as involving discrete intermediates that undergo an ordinary competition between subsequent pathways to form the observed products. The combined experimental, computational, and dynamic trajectory study here suggests that this view is incorrect, and that solvation dynamics plays a critical role in the mechanism. While implicit solvent models were inadequate, QM/QM' trajectories in explicit solvent provide an accurate prediction of the experimental selectivity in the addition of HCl to 1,3-pentadiene. Trajectories initiated from a protonation saddle point on the potential of mean force surface are predominantly unproductive due to a gating effect of solvation that allows diene protonation only when the incipient ion pair is neither too solvent-stabilized nor too little. Protonation then leads to relatively unsolvated ion pairs, and a majority of these collapse rapidly to the 1,2-product, without barrier and without achieving equilibrium solvation as intermediates. The remainder decay slowly, at a rate consistent with equilibrium solvation as true intermediates, affording a mixture of addition products. Overall, an accurate description of the nature and pathway selectivity of the ion pair intermediates in carbocation reactions must allow for species lacking equilibrium solvation. Potential reinterpretations of a series of historically notable observations in carbocation reactions are discussed.
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