当前位置: X-MOL 学术Inorg. Chem. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Hydroboration of CO2 to Methyl Boronate Catalyzed by a Manganese Pincer Complex: Insights into the Reaction Mechanism and Ligand Effect
Inorganic Chemistry ( IF 4.6 ) Pub Date : 2022-03-31 , DOI: 10.1021/acs.inorgchem.2c00285
Lin Zhang 1 , Yaqi Zhao 2 , Chong Liu 2 , Min Pu 2 , Ming Lei 2 , Zexing Cao 1
Affiliation  

The conversion of carbon dioxide to fuels, polymers, and chemicals is an attractive strategy for the synthesis of high-value-added products and energy-storage materials. Herein, the density functional theory method was employed to investigate the reaction mechanism of CO2 hydroboration catalyzed by manganese pincer complex, [Mn(Ph2PCH2SiMe2)2NH(CO)2Br]. The carbonyl association and carbonyl dissociation mechanisms were investigated, and the calculated results showed that the carbonyl association mechanism is more favorable with an energetic span of 27.0 kcal/mol. Meanwhile, the solvent effect of the reaction was explored, indicating that the solvents could reduce the catalytic activity of the catalyst, which was consistent with the experimental results. In addition, the X ligand effect (X = CO, Br, H, PH3) on the catalytic activity of the manganese complex was explored, indicating that the anionic complexes [MnI – Br] and [MnI – H] have higher catalytic activity. This may not only shed light on the fixation and conversion of CO2 catalyzed by earth-abundant transition-metal complexes but also provide theoretical insights to design new transition-metal catalysts.

中文翻译:

锰钳络合物催化 CO2 硼氢化成硼酸甲酯:反应机理和配体效应的见解

将二氧化碳转化为燃料、聚合物和化学品是合成高附加值产品和储能材料的一种有吸引力的策略。本文采用密度泛函理论方法研究了锰钳配合物[Mn(Ph 2 PCH 2 SiMe 2 ) 2 NH(CO) 2催化CO 2硼氢化反应的机理。溴]。研究了羰基缔合和羰基解离机理,计算结果表明羰基缔合机理更有利,能量跨度为27.0 kcal/mol。同时探讨了反应的溶剂效应,表明溶剂会降低催化剂的催化活性,这与实验结果一致。此外,探讨了X配体效应(X = CO、Br、H、PH 3)对锰络合物催化活性的影响,表明阴离子络合物[Mn I - Br] -和[Mn I - H] -具有较高的催化活性。这不仅可以阐明 CO 2的固定和转化由地球上丰富的过渡金属配合物催化,但也为设计新的过渡金属催化剂提供了理论见解。
更新日期:2022-03-31
down
wechat
bug