Mechanism of Regioselective Ring-Opening Reactions of 1,2-Epoxyoctane Catalyzed by Tris(pentafluorophenyl)borane: A Combined Experimental, Density Functional Theory, and Microkinetic Study
| Autor: | Justin M. Notestein, Mihir N. Bhagat, Ying Yu, Linda J. Broadbelt, Youlong Zhu, Hirsekorn Kurt F, SonBinh T. Nguyen, Arjun Raghuraman |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Reaction mechanism
Materials science 010405 organic chemistry Regioselectivity General Chemistry Borane 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences Reaction rate chemistry.chemical_compound chemistry Computational chemistry Tris(pentafluorophenyl)borane Density functional theory Reactivity (chemistry) |
| Zdroj: | ACS Catalysis. 8:11119-11133 |
| ISSN: | 2155-5435 |
| Popis: | A nonconventional, water-mediated catalytic mechanism was proposed to explain the effects of residual water on the reactivity and regioselectivity of tris(pentafluorophenyl)borane catalyst in the ring-opening reaction of 1,2-epoxyoctane by 2-propanol. This nonconventional mechanism was proposed to operate in parallel with conventional Lewis acid-catalyzed ring-opening. Microkinetic modeling was conducted to validate the proposed reaction mechanism, with all kinetic and thermodynamic parameters derived from density functional theory (DFT) calculations. Experimental data at a variety of temperatures and water contents were captured by the model after adjustments within reasonable limits set by experimental benchmarking and accuracy of theory of a small subset of parameters. In addition, the microkinetic model was able to generate accurate predictions at reaction conditions that were not used for parameter estimation. Detailed analysis of the net reaction rates showed that >95% of the reaction flux passed th... |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|