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A DFT-design of single component bifunctional organocatalysts for the carbon dioxide/propylene oxide coupling reaction
Physical Chemistry Chemical Physics ( IF 3.3 ) Pub Date : 2021-11-08 , DOI: 10.1039/d1cp04091j
Morad M El-Hendawy 1 , Ibtesam M Desoky 1 , Mahmoud M A Mohamed 1
Affiliation  

The aim of this work is to develop single-component bifunctional organic catalysts capable of effective coupling reactions between CO2 and propylene epoxide (PO) under mild conditions using density functional theory (DFT) calculations. The dual functionalities of the target catalysts come from their inclusion of a hydroxyl-containing electrophile and the nucleophilicity of iodide ion. In this respect, a series of hydroxyl-functionalized quaternary onium-based ionic liquids were studied using M062X-D3/def2-TZVP//M062X-D3/def2-SVPP model chemistry. The design of catalysts was based on tailoring two structural factors; the first one is the onium center of pnictogens (N, P, As, Sb and Bi), and the second one is the number of hydrogen bond donor groups (n = 1–3). The proposed catalysts were examined by investigation of their catalytic mechanisms to afford the cyclic carbonate. Additionally, the highest active transition state, along with the potential energy difference, was examined using non-covalent interaction (NCI) analysis. Also, the activation strain model (ASM) was used to explain the kinetic behavior of PO activation. The findings showed that the ring-opening step of PO is always the critical step of the reaction. Among the suggested catalysts, the results indicated that the dihydroxyl ammonium-based catalyst (2OH-NI) is a good choice for this catalysis under mild and solvent-free conditions.

中文翻译:

用于二氧化碳/环氧丙烷偶联反应的单组分双功能有机催化剂的 DFT 设计

这项工作的目的是开发能够在温和条件下使用密​​度泛函理论 (DFT) 计算在CO 2和环氧丙烷 ( PO )之间进行有效偶联反应的单组分双功能有机催化剂。目标催化剂的双重功能来自于它们包含含羟基的亲电试剂和碘离子的亲核性。在这方面,使用 M062X-D3/def2-TZVP//M062X-D3/def2-SVPP 模型化学研究了一系列羟基官能化季铵基离子液体。催化剂的设计基于定制两个结构因素;第一个是 pnictogens(N、P、As、Sb 和 Bi)的鎓中心,第二个是氢键供体基团的数量(n= 1–3)。通过研究它们提供环状碳酸酯的催化机制来检查所提出的催化剂。此外,使用非共价相互作用 (NCI) 分析检查最高活性过渡态以及势能差。此外,活化应变模型 (ASM) 用于解释PO活化的动力学行为。结果表明,PO的开环步骤始终是反应的关键步骤。在推荐的催化剂中,结果表明二羟基铵基催化剂 (2OH-NI) 在温和和无溶剂条件下是该催化的良好选择。
更新日期:2021-11-26
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