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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Description of the Reaction Intermediate Stabilization for the Zimmerman Di-pi-methane Rearrangement on the Basis of a Parametric Diabatic Analysis
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Description of the Reaction Intermediate Stabilization for the Zimmerman Di-pi-methane Rearrangement on the Basis of a Parametric Diabatic Analysis

机译：基于参数化糖尿病分析，对Zimmerman Di-Pi-甲烷重排的反应中间稳定化的描述

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摘要

The mechanism of the Zimmerman di-pi-methane rearrangement has been studied using a parametric diabatic analysis (PDA) on which the diagonal elements on the effective Hamiltonian defining the energies of the diabatic electronic states have been parametrized and modeled upon the use of the vertex form of a parabolic function. The PDA requires two inputs: the energy local minimum of an optimized structure along the intrinsic reaction coordinate and the maximum gradients associated with the barriers for the transition states. In the present work, the PDA was used to gain novel insights into the mechanism of the triplet di-pi-methane rearrangement of substituted dibenzobarrelenes. Our results suggest that, when using an electron-withdrawing group as substituent, the activation energy for the rate-determining step is directly modulated by the stabilization of the biradical intermediate on the triplet surface. This mechanistic feature was thoroughly analyzed and discussed within the conceptual framework provided by the diabatic model of intermediate stabilization (DMIS).
机译：已经研究了Zimmerman Di-Pi-甲烷重新排列的机制，使用了参数化糖尿病分析（PDA），在该参数上的哈米尼尔（PDA）上有效地定义了糖尿病电子状态的能量的对角线元件已经参数化和建模在使用顶点抛物线功能的形式。 PDA需要两个输入：沿着内在反应坐标的优化结构的能量局部最小，以及与转换状态的屏障相关联的最大梯度。在本作工作中，PDA用于获得进入取代的Dibentobarrenes的三重态Di-Pi-甲烷重排机制的新颖见解。我们的研究结果表明，当使用吸电子基团作为取代基时，通过在三重态表面上的抗体中间体的稳定性直接调节速率确定步骤的激活能量。在中间稳定（DMIS）的酸性模型提供的概念框架内彻底分析和讨论了该机制特征。

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