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• W1944022460 abstract "Bimolecular elimination reactions (E2) are fundamentally important processes in organic chemistry. Our current work focuses on a computational investigation of several interesting and unexpected experimental results previously obtained in our laboratory. In particular, we have examined the detailed mechanisms for generating CH 2 CHO − from the reaction of HO − + CH 3 CH 2 OCH 2 CH 2 OCH 3 , the unusually large isotope effect ( k H / k D = 5.5) for the reaction of NH 2 − + CH 3 CH 2 OCH 2 CH 3 , and the possible kinetic barriers in the reaction of H − + CH 3 CH 2 OCH 2 CH 3 . Moreover, we have explored the high site selectivity in the reaction of NH 2 − + CH 3 CH 2 OC(CH 3 ) 3 . In the HO − + CH 3 CH 2 OCH 2 CH 2 OCH 3 reaction, three ion-neutral encounter complexes were located and fully optimized. The corresponding transition states were confirmed during the first E2 hydrogen-transfer process and they all possess E1 cb -like antiperiplanar conformations. The formation of loosely bonded CH 3 O − and H 2 O moieties was found to be essential for the second E2-type hydrogen transfer, and an intriguing E1 cb -like gauche transition state (CH 3 OH–C α –C β –OCHCH 2 dihedral = 40.9°) was located, which results in the formation of ionic CH 2 CHO − and neutral CH 3 OH, H 2 O, and C 2 H 4 products. The lowest kinetic barrier for the reaction of NH 2 − + CH 3 CH 2 OCH 2 CH3 is −5.3 kcal mol −1 (–22.2 kJ mol −1 ), which is 1.5 kcal mol −1 (6.3 kJ mol −1 ) higher in energy than the lowest barrier for the reaction HO − + CH 3 CH 2 OCH 2 CH3. The higher kinetic barrier of the NH 2 − + CH 3 CH 2 OCH 2 CH 3 reaction is consistent with the observation of a larger isotope effect. The lowest kinetic barrier for the reaction of H − + CH 3 CH 2 OCH 2 CH 3 is +5.4 kcal mol −1 (22.6 kJ mol −1 ), indicating that, although H − is a strong base, this reaction cannot occur at room temperature, which agrees well with the experimental results. The high selectivity in the formation of CH 3 CH 2 O − from the reaction of NH 2 − + CH 3 CH 2 OC(CH 3 ) 3 is explained by an electrostatic potential analysis of the ether molecule. Thus, this computational study provides important insight into the detailed mechanisms of elimination reactions." @default.
• W1944022460 created "2016-06-24" @default.
• W1944022460 creator A5020222140 @default.
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• W1944022460 date "2015-06-01" @default.
• W1944022460 modified "2023-09-27" @default.
• W1944022460 title "Computational Studies of the Gas Phase Reactions of Ethers with Anions: Kinetic Barriers, Isotope Effects, Consecutive Eliminations and Site Selectivity" @default.
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• W1944022460 doi "https://doi.org/10.1255/ejms.1351" @default.
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