Cation-assisted interactions between N-heterocycles and CO2
Cation-assisted interactions between N-heterocycles and CO2
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N-杂环和 CO2 之间的阳离子辅助相互作用
DOI：
10.1039/c5cp01793a
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发表时间：
2015
影响因子：
3.3
通讯作者：
C. Wu
中科院分区：
文献类型：
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作者：
H. Tang;D. Lu;C. Wu
采用密度泛函理论（DFT）方法系统研究了含氮杂环与CO2的阳离子辅助相互作用。对于中性和阴离子（非类卡宾）NHC，单价阳离子（即，碱金属离子）是中等至小（NHC-CO2结合能变化，ΔBE通常< 25 kJ mol−1）。然而，对于NHC卡宾，由于其强碱性，影响很强（ΔBE > 60 kJ mol−1），单价阳离子在二卡宾与CO2的单羧化中起着关键作用。相比之下，二价碱土金属阳离子，由于其较小的尺寸和较高的形式电荷，表现出更强的影响（ΔBE > 100 kJ mol−1）。二价阳离子应被纳入下一代CO2捕获试剂。其他方面包括反应势能面（PES），基于轨道的相互作用分析，取代效应和反应性描述符（阳离子大小，反应N孤对轨道能量等）。也进行了详细的讨论。
Cation-assisted interactions between N-containing heterocycles (NHCs) and CO2 have been systematically studied by using density functional theory (DFT). For neutral and anionic (non-carbenoid) NHCs, the effects of monovalent cations (i.e., alkali metal ions) are moderate to small (the NHC–CO2 binding energy change, ΔBE usually < 25 kJ mol−1). However, for NHC carbenes, due to their strong basicity, the effects are strong (ΔBE > 60 kJ mol−1) and the monovalent cations play a critical role in the single carboxylation of dicarbenes with CO2. In comparison, divalent alkali earth metal cations, due to both their smaller sizes and higher formal charges, exhibit a much stronger influence (ΔBE > 100 kJ mol−1). Divalent cations should be incorporated into next generation CO2 capture reagents. Other aspects including the reaction potential energy surface (PES), orbital-based analyses of interactions, substitution effects, and the reactivity descriptors (cation size, reacting N lone pair orbital energy, etc.) have been discussed in detail as well.