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锂和镁卡宾环丙烷化反应机理：金属-π和σ相互作用

Reaction Mechanism of Li and Mg Carbenoid Cyclopropanations: Metal-π and σ Interactions.

作者信息

Villablanca Daniel, Durán Rocio, Lamsabhi Al Mokhtar, Herrera Barbara

机构信息

Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Santiago 7820436, Región Metropolitana, Chile.

Departamento de Química, Facultad de Ciencias, Módulo 13 and Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Madrid 28049, Spain.

出版信息

ACS Omega. 2019 Nov 8;4(21):19452-19461. doi: 10.1021/acsomega.9b02905. eCollection 2019 Nov 19.

DOI:10.1021/acsomega.9b02905
PMID:31763569
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6868892/
Abstract

The mechanism of the reaction of lithium and magnesium carbenoids with ethylene to give cyclopropane has been explained in detail in all the steps at the G4 level of theory. We explored the lithium and magnesium interaction toward π and σ bonds in the reactants and the products. We have also investigated the reaction path by means of the force profile formalism in order to highlight the electronic and the structural rearrangements along the potential energy surface of the cyclopropanation. The results indicate that all of the reactions are stepwise, exoenergetic, with low barriers. All our findings were confirmed by dynamic simulations for chlorometal carbenoids. Furthermore, from the intrinsic reaction coordinate procedure, we were able to find out the intermediates that can take place when the reaction is descending from the transition state to the products or reactants. The reaction force analysis at B3LYP/6-311G(d,p) indicates that the energy barriers are mostly due to structural rearrangements which are produced by the approach of the carbenoid to ethylene. Quantum theory of atoms in molecules and electron localization function analyses indicate that products, reactants, and intermediates form complexes stabilized by attractive forces between Li/Mg and single/double bonds.

摘要

锂和镁卡宾与乙烯反应生成环丙烷的反应机理已在G4理论水平上的所有步骤中得到详细解释。我们研究了锂和镁与反应物和产物中π键和σ键的相互作用。我们还通过力轮廓形式法研究了反应路径，以突出环丙烷化势能面上的电子和结构重排。结果表明，所有反应都是分步的、放热的，且势垒较低。我们所有的发现都通过氯金属卡宾的动力学模拟得到了证实。此外，通过内禀反应坐标程序，我们能够找出反应从过渡态降至产物或反应物时可能出现的中间体。在B3LYP/6-311G(d,p)水平上的反应力分析表明，能垒主要是由于卡宾接近乙烯时产生的结构重排。分子中原子的量子理论和电子定域函数分析表明，产物、反应物和中间体形成了由Li/Mg与单键/双键之间的吸引力稳定的络合物。

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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dd2/6868892/20e9489a75ff/ao9b02905_0005.jpg
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本文引用的文献

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