Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO2 Into Valuable Chemicals

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Mohmmad Faizan, Guntupalli Santhosh, Madhumita Chakraborty, Ravinder Pawar
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Abstract

The conversion of CO2 into valuable chemicals remains a significant challenge for achieving environmental sustainability, primarily due to the stability of the CO2 molecule. This necessitates the development of efficient and ecofriendly catalysts. In recent years, frustrated Lewis pairs (FLPs) have shown promise for CO2 utilization. In this study, we introduce α-aminodiboronic acid (DBA), a novel trifunctional aminoboronic acid, as an intramolecular FLP for converting CO2 into cyclic carbonate and formic acid. Using density functional theory (DFT) calculations, we explored the reaction mechanism and investigated DBA's electronic structure through molecular electrostatic potential surface (MESP) and natural bond orbital (NBO) analyses. Our results reveal that one −B (OH)2 group induces an unusual state of frustration in the molecule due to charge transfer from the nitrogen atom's lone pair to the π* orbitals, enhancing catalytic performance. The additional −B (OH)2 group serves as an anchoring site for reactive species. The epoxide activation energy is reduced by approximately 27 kcal/mol compared to the uncatalyzed reaction, and the reduction of CO2 occurs with a requirement of 26 kcal/mol. The additional −B (OH)2 plays a crucial role in the catalytic mechanism and minimizes the energies of various structures observed in the reaction path. The reaction energetics align with structural analysis observations, marking this study as the first report on single-molecule trifunctional FLPs for transforming CO2 into valuable chemicals.

Abstract Image

由氨基硼酸衍生的新型三官能团分子内受托路易斯对,可将二氧化碳转化为有价值的化学品
主要由于二氧化碳分子的稳定性,将二氧化碳转化为有价值的化学品仍然是实现环境可持续性的重大挑战。这就需要开发高效、环保的催化剂。近年来,受挫路易斯对(FLPs)在二氧化碳利用方面显示出了前景。在本研究中,我们引入了α-氨基二硼酸(DBA)--一种新型的三官能氨基硼酸--作为分子内 FLP,用于将 CO2 转化为环碳酸盐和甲酸。利用密度泛函理论(DFT)计算,我们探索了反应机理,并通过分子静电位面(MESP)和天然键轨道(NBO)分析研究了 DBA 的电子结构。我们的研究结果表明,由于电荷从氮原子的孤对向π*轨道转移,一个-B (OH)2基团在分子中引起了一种不寻常的沮度状态,从而提高了催化性能。附加的 -B (OH)2 基团可作为反应物的锚定位点。与未催化反应相比,环氧化物的活化能降低了约 27 kcal/mol,而 CO2 的还原只需要 26 kcal/mol。附加的 -B (OH)2 在催化机理中起着关键作用,并使反应路径中观察到的各种结构的能量最小化。反应能量与结构分析观测结果一致,这标志着这项研究首次报道了将 CO2 转化为有价值化学品的单分子三功能 FLPs。
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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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