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Exploring the conformational space of cobalt(III)-salen catalyst for CO2 /epoxide copolymerization: Effect of quaternary ammonium salts on preference of alternative isomers
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2018-06-11 , DOI: 10.1002/jcc.25358 Karol Dyduch 1 , Monika Srebro‐Hooper 1 , Bun Yeoul Lee 2 , Artur Michalak 1
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2018-06-11 , DOI: 10.1002/jcc.25358 Karol Dyduch 1 , Monika Srebro‐Hooper 1 , Bun Yeoul Lee 2 , Artur Michalak 1
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Model catalysts for CO2/epoxide copolymerization based on Co(III) complexes were studied, with focus on the preference of their alternative isomers, cisβ vs. trans. The systems range from model structures without the co‐catalyst, as derived from crystallographic data, to complex models with two (CH2)4N+R3 co‐catalyst chains (R = Me, Bu) grafted onto a Co(III)–salcy core. To explore the conformational space of the latter complexes, a computational protocol was developed, combining a systematic model‐building approach with static and molecular dynamics calculations, and multilevel energy assessment (PM7 and DFT). Results demonstrate an influence of the co‐catalyst on the relative stability of the isomers. The cisβ isomer is preferred for complexes without N+‐chains and the cisβ ↔ trans isomerization is feasible. Five‐coordinate species and open‐shell electronic configurations are energetically disfavored. The cisβ preference decreases with the introduction and enlargement of (CH2)4N+R3: both isomers can be populated for R = Me, while the trans isomer is visibly preferred for R = Bu. © 2018 Wiley Periodicals, Inc.
中文翻译：
探索用于 CO2/环氧化物共聚的钴 (III)-salen 催化剂的构象空间：季铵盐对替代异构体偏好的影响
研究了基于 Co(III) 配合物的 CO2/环氧化物共聚的模型催化剂，重点是其替代异构体顺式与反式的偏好。该系统的范围从没有助催化剂的模型结构（从晶体学数据得出），到具有两个 (CH2)4N+R3 助催化剂链（R = Me，Bu）接枝到 Co(III)-salcy 上的复杂模型核。为了探索后一种复合物的构象空间，开发了一种计算协议，将系统模型构建方法与静态和分子动力学计算以及多级能量评估（PM7 和 DFT）相结合。结果表明助催化剂对异构体的相对稳定性有影响。对于没有 N+ 链的复合物，顺式β 异构体是首选，顺式β ↔ 反式异构化是可行的。五坐标物种和开壳电子配置在能量上是不受欢迎的。随着 (CH2)4N+R3 的引入和扩大，顺式β 偏好降低：两种异构体都可以填充 R = Me，而反式异构体明显首选 R = Bu。© 2018 Wiley Periodicals, Inc.
更新日期：2018-06-11
中文翻译：
探索用于 CO2/环氧化物共聚的钴 (III)-salen 催化剂的构象空间：季铵盐对替代异构体偏好的影响
研究了基于 Co(III) 配合物的 CO2/环氧化物共聚的模型催化剂，重点是其替代异构体顺式与反式的偏好。该系统的范围从没有助催化剂的模型结构（从晶体学数据得出），到具有两个 (CH2)4N+R3 助催化剂链（R = Me，Bu）接枝到 Co(III)-salcy 上的复杂模型核。为了探索后一种复合物的构象空间，开发了一种计算协议，将系统模型构建方法与静态和分子动力学计算以及多级能量评估（PM7 和 DFT）相结合。结果表明助催化剂对异构体的相对稳定性有影响。对于没有 N+ 链的复合物，顺式β 异构体是首选，顺式β ↔ 反式异构化是可行的。五坐标物种和开壳电子配置在能量上是不受欢迎的。随着 (CH2)4N+R3 的引入和扩大，顺式β 偏好降低：两种异构体都可以填充 R = Me，而反式异构体明显首选 R = Bu。© 2018 Wiley Periodicals, Inc.
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