Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture.
Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture.
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作者：
使用密度泛函理论检查钴萨伦配合物的亲核性质，以研究其固碳能力。特别是，考虑了二氧化碳对中性和阴离子钴萨伦分子的攻击。阴离子钴 salen 络合物发生碳固定，这是由于钴中心和二氧化碳分子之间在 Co dz2-CO2 π* 相互作用中的亲核相互作用所致。通过微动弹性带计算进行的最小能量路径搜索显示，阴离子络合物的正向活化能低于中性络合物，这表明阴离子络合物的形成在热力学和动力学上是有利的。在这种情况下，当观察到从钴中心到二氧化碳的部分电荷转移时，CO2 分子被化学吸附。所提出的反应机制解释了如何通过苯环上给电子或吸电子基团的适当取代来调节CO2-钴salen络合物的Co-C键能。使用密度泛函理论检查钴萨伦配合物的亲核性质，以研究其固碳能力。
The nucleophilic properties of cobalt salen complexes are examined using density functional theory to investigate its carbon fixing capacity. In particular, carbon dioxide attack on neutral and anionic cobalt salen molecules is considered. Carbon fixation occurs for the anionic cobalt salen complex and is due to the nucleophilic interaction between the cobalt center and carbon dioxide molecule in a Co dz2–CO2 π* interaction. A minimum energy path search by a nudged elastic band calculation reveals a lower forward activation energy for the anionic complex than the neutral complex, indicating that the formation of the anionic complex is thermodynamically and kinetically favored. In this case, the CO2 molecule is chemisorbed as partial charge transfer from the cobalt center to carbon dioxide is observed. Proposed reaction mechanisms explain how the Co–C bond energy of the CO2–cobalt salen complex can be tuned by appropriate substitutions of electron donating or withdrawing groups on the phenyl ring. The nucleophilic properties of cobalt salen complexes are examined using density functional theory to investigate its carbon fixing capacity.
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