The SFI Strategic Research Cluster in Solar Energy Conversion and the Center for Synthesis and Chemical Biology, School of Chemical and Bioprocess Engineering, University College Dublin, Belfield, Dublin 4, Ireland.
J Mol Model. 2011 Dec;17(12):3151-62. doi: 10.1007/s00894-011-0965-z. Epub 2011 Mar 2.
This paper investigates the thermodynamics of gas-phase CO(2) cascade uptake-reactions in the form of carbonate or monomethylcarbonate anions in the host cavity of various dinuclear octa-azacryptates of m-CH(2)C(6)H(4)CH(2) and 2,5-furano-spaced hosts, L (1) and L (2) cryptands, using density functional theory (DFT). The cascade process involves two stages, namely the formation of dinuclear cryptate complexes, and the subsequent formation of either μ-carbonato cryptate complexes or μ-monomethylcarbonato cryptates. The geometric and electronic structures were also investigated to determine the parameters that affect the stability of the complexes. Natural bond orbital (NBO) analysis was used to investigate the interactions between the trapped anion and its host. Ion selectivity was studied in terms of the formation of dinuclear cryptate complexes, while the basicity and nucleophilicity of cryptands towards Lewis acids was also studied, and good agreement was found vis-à-vis available experimental data.
本文使用密度泛函理论（DFT）研究了在各种双核八氮杂冠醚主体空腔中，以碳酸盐或单甲基碳酸盐阴离子形式存在的气相 CO(2)级联吸收反应的热力学。主体空腔为 m-CH(2)C(6)H(4)CH(2) 和 2,5-呋喃间隔的 L(1)和 L(2)穴醚配体。级联过程包括两个阶段，即双核穴醚配合物的形成，以及随后形成μ-碳酸盐穴醚配合物或μ-单甲基碳酸盐穴醚配合物。还研究了几何和电子结构，以确定影响配合物稳定性的参数。自然键轨道（NBO）分析用于研究被捕获阴离子与其主体之间的相互作用。离子选择性是根据双核穴醚配合物的形成来研究的，同时还研究了穴醚对路易斯酸的碱性和亲核性，并且与可用的实验数据吻合良好。
