Abstract

CO₂ is an important carbon resource, which could be chemically utilized by carboxylation. In this paper, the carboxylation between benzene polycarboxylic acids (BPCAs) and CO₂ was conducted using Cs₂CO₃ as a catalyst. The relationship between the product distribution and Mulliken charge at the reaction site of BPCAs was explored by combining experiments and quantum chemical calculations of molecular properties in the reaction of carboxylation between BPCAs and CO₂. The negative Mulliken charge was found to facilitate carboxylation at the reaction site of BPCAs. Hydrogen abstraction was the rate-determining step for carboxylation, and its energy barrier was calculated for different C–H in the BPCA molecule. The results showed that the C–H bond with the more negative Mulliken charge was more easily deprotonated, which further verified the above conclusion. The study provides a convenient approach to predict a product distribution for carboxylation between BPCAs and CO₂ according to the Mulliken charge of BPCAs.

中文翻译：

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深入探讨苯多羧酸与CO2羧化反应中产物分布与分子性质的关系

摘要

CO ₂是一种重要的碳资源，可通过羧化进行化学利用。本文以Cs ₂ CO ₃为催化剂，进行了苯多羧酸(BPCA)与CO ₂的羧化反应。通过结合BPCA与CO ₂羧化反应中分子性质的实验和量子化学计算，探讨了BPCA反应位点的产物分布与Mulliken电荷之间的关系。发现马利肯负电荷有利于 BPCA 反应位点的羧化。夺氢是羧化的决定速率步骤，其能垒是针对 BPCA 分子中不同的 C-H 进行计算的。结果表明，Mulliken负电荷越多的C-H键更容易去质子化，进一步验证了上述结论。该研究提供了一种根据 BPCA 的 Mulliken 电荷来预测 BPCA 和 CO ₂之间羧化产物分布的便捷方法。