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Potential Energy Surfaces of Vinylogous Wolff Rearrangement: NBO Analysis and Molecular Dynamic Simulation
ChemistryOpen ( IF 2.3 ) Pub Date : 2021-08-06 , DOI: 10.1002/open.202100049
Hossein Taherpour Nahzomi 1 , Faten Divsar 1
Affiliation  

The potential energy surfaces of the Vinylogous Wolff Rearrangement, an alternative process for the Wolff Rearrangement that takes place β,γ-unsaturated diazoketones have been fully explored employing M062X model chemistry and in a complementary task by means of the CASSCF method. The NBO analysis has been invoked to reveal the alternations of orbital occupancies and their stabilization energies through some of the critical structures located on the pathways. The calculations establish a two steps process for each pathway involving a second higher energy transition state that seems likely to be the rate determining step in agreement with experimental results. Energy analysis indicates more feasibility of the pathway including diradical intermediate. The most striking feature of the study concerns the finding out a transition state providing a channel in between two pathways through interconversion of the two keys bicyclo[2.1.0]pentanone and diradical intermediates.

中文翻译:

Vinylogous Wolff 重排的势能面:NBO 分析和分子动力学模拟

Vinylogous Wolff 重排的势能表面是发生 β,γ-不饱和重氮酮的 Wolff 重排的替代过程,已使用 M062X 模型化学和通过 CASSCF 方法的补充任务进行了充分探索。NBO 分析已被用来通过位于路径上的一些关键结构来揭示轨道占用的交替及其稳定能量。计算为涉及第二个更高能量过渡态的每个途径建立了一个两步过程,这似乎可能是与实验结果一致的速率确定步骤。能量分析表明包括双自由基中间体的途径更具可行性。
更新日期:2021-10-01
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