دورية أكاديمية
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Revisiting Textbook Azide-Clock Reactions: A "Propeller-Crawling" Mechanism Explains Differences in Rates.

التفاصيل البيبلوغرافية
العنوان: Revisiting Textbook Azide-Clock Reactions: A "Propeller-Crawling" Mechanism Explains Differences in Rates.
المؤلفون: Bogetti AT; Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States., Zwier MC; Department of Chemistry, Drake University, Des Moines, Iowa 50311, United States., Chong LT; Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
المصدر: Journal of the American Chemical Society [J Am Chem Soc] 2024 May 08; Vol. 146 (18), pp. 12828-12835. Date of Electronic Publication: 2024 Apr 30.
نوع المنشور: Journal Article
اللغة: English
بيانات الدورية: Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: PubMed not MEDLINE; MEDLINE
أسماء مطبوعة: Publication: Washington, DC : American Chemical Society
Original Publication: Easton, Pa. [etc.]
مستخلص: An ongoing challenge to chemists is the analysis of pathways and kinetics for chemical reactions in solution, including transient structures between the reactants and products that are difficult to resolve using laboratory experiments. Here, we enabled direct molecular dynamics simulations of a textbook series of chemical reactions on the hundreds of ns to μs time scale using the weighted ensemble (WE) path sampling strategy with hybrid quantum mechanical/molecular mechanical (QM/MM) models. We focused on azide-clock reactions involving addition of an azide anion to each of three long-lived trityl cations in an acetonitrile-water solvent mixture. Results reveal a two-step mechanism: (1) diffusional collision of reactants to form an ion-pair intermediate; (2) "activation" or rearrangement of the intermediate to the product. Our simulations yield not only reaction rates that are within error of experiment but also rates for individual steps, indicating the activation step as rate-limiting for all three cations. Further, the trend in reaction rates is due to dynamical effects, i.e., differing extents of the azide anion "crawling" along the cation's phenyl-ring "propellers" during the activation step. Our study demonstrates the power of analyzing pathways and kinetics to gain insights on reaction mechanisms, underscoring the value of including WE and other related path sampling strategies in the modern toolbox for chemists.
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معلومات مُعتمدة: R01 GM111805 United States GM NIGMS NIH HHS; R01 GM115185 United States GM NIGMS NIH HHS; R01 GM115805 United States GM NIGMS NIH HHS
تواريخ الأحداث: Date Created: 20240430 Latest Revision: 20240512
رمز التحديث: 20240512
مُعرف محوري في PubMed: PMC11078601
DOI: 10.1021/jacs.4c03360
PMID: 38687173
قاعدة البيانات: MEDLINE
الوصف
تدمد:1520-5126
DOI:10.1021/jacs.4c03360