Computer-aided rational design of Fe(III)-catalysts for the selective formation of cyclic carbonates from CO2 and internal epoxides,Catalysis Science & Technology

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Computer-aided rational design of Fe(III)-catalysts for the selective formation of cyclic carbonates from CO2 and internal epoxides
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2017-08-24 00:00:00 , DOI: 10.1039/c7cy01435j
Indranil Sinha _{1,

2,

3,

4,

5} , Yuseop Lee _{3,

4,

5,

6} , Choongman Bae _{3,

4,

5,

6} , Samat Tussupbayev _{1,

2,

3,

4,

5} , Yujin Lee _{1,

2,

3,

4,

5} , Min-Seob Seo _{3,

4,

5,

6} , Jin Kim _{3,

4,

5,

6} , Mu-Hyun Baik _{1,

2,

3,

4,

5} , Yunho Lee _{1,

2,

3,

4,

5} , Hyunwoo Kim _{3,

4,

5,

6}

Affiliation

The catalytic mechanism of the cyclic carbonate formation reaction between CO₂ and internal epoxides promoted by Fe-salen and the Kleij catalyst was examined in detail to better understand how the catalytic efficiency can be increased. Specifically, we aimed to make the catalyst more chemoselective towards forming cyclic carbonates and preventing the competing side reaction leading to polycarbonates via ring-opening polymerization. A few rational design principles were derived and first tested using computer models based on density functional theory. The most promising candidate that was identified in the computer model was then prepared and found to display significantly enhanced reactivity towards forming the cyclic carbonates, supporting the validity of the mechanistic insights deduced from the computer simulations. We propose that a cyclic carbonate is formed most efficiently via an inner-sphere mechanism where both the CO₂ and epoxide substrates utilize the metal center for the key bond forming events. In contrast, the ring-opening polymerization uses an outer-sphere mechanism, where a carbonate attacks and ring-opens the epoxide bound to the metal without engaging the metal directly. These mechanistic differences are exploited to implement a chemoselective catalyst by enhancing the rate of the cyclic carbonate formation reaction while leaving the polymerization pathway largely unaffected.

中文翻译：

Fe（III）催化剂的计算机辅助合理设计，用于从CO ₂和内部环氧化物选择性形成环状碳酸酯

详细研究了Fe-salen和Kleij催化剂促进的CO ₂与内部环氧化物之间环状碳酸酯形成反应的催化机理，以更好地理解如何提高催化效率。具体而言，我们旨在使催化剂对形成环状碳酸酯更具化学选择性，并防止通过开环聚合。得出了一些合理的设计原理，并首先使用基于密度泛函理论的计算机模型进行了测试。然后准备了在计算机模型中确定的最有前途的候选物，发现它显示出显着增强的对形成环状碳酸酯的反应性，从而支持了从计算机模拟中得出的机理见解的有效性。我们建议通过内球机理最有效地形成环状碳酸酯，其中两个CO ₂环氧化物基材利用金属中心进行键键形成事件。相反，开环聚合使用外球机理，其中碳酸盐侵蚀并开环结合到金属上的环氧化物，而不直接与金属结合。利用这些机理上的差异，可通过提高环状碳酸酯形成反应的速率来实现化学选择性催化剂，同时又不影响聚合路径。

更新日期：2017-09-11

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