To provide guiding information for developing efficient catalysts for CO₂ carboxylation, we investigated the mechanism of asymmetric reductive carboxylation of N-(2-bromophenyl)-N-methylmethacrylamide with CO₂ catalyzed by a nickel complex using density functional theory (DFT) calculations. The reaction was found to proceed via a multistep and elaborate mechanism. Additionally, CO₂ exhibits a preference for inserting into the Ni(I) intermediate rather than Ni(II) intermediate. The noncovalent interaction (NCI) analysis reveals that the π-π stacking interactions and hydrogen bonding interactions lead to the stereoselectivity.

中文翻译：

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镍配合物催化 N-(2-溴苯基)-N-甲基甲基丙烯酰胺与 CO2 不对称还原羧化反应的理论研究

为了为开发高效的CO _{2羧化催化剂提供指导信息，我们}利用密度泛函理论（DFT）计算研究了镍配合物催化的N-(2-溴苯基) -N-甲基甲基丙烯酰胺与CO ₂的不对称还原羧化反应机理。人们发现该反应是通过多步骤和复杂的机制进行的。此外，CO ₂表现出优先插入Ni(I)中间体而不是Ni(II)中间体。非共价相互作用（NCI）分析表明，π-π堆积相互作用和氢键相互作用导致了立体选择性。