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首页> 外文期刊>ACS Omega >Isomers of Alkali Metal (Methylbenzyl)allylamides: A Theoretical Perspective
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Isomers of Alkali Metal (Methylbenzyl)allylamides: A Theoretical Perspective

机译：碱金属（甲基苄基）烯丙酰胺的异构体：理论透视

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Recent studies of alkali metal N -(α-methylbenzyl)allylamides containing lithium, sodium, and potassium have shown unique rearrangements in NMR experiments. It was found that lithium isomers favored the formation of aza-allyl and aza-enolate complexes that could exist in a solution for a substantial amount of time. As the radius of the metal ion increases going from lithium to potassium, so does the preference for the formation of the imine structure. For sodium, the aza-allyl complex could still be isolated, whereas the imine structure was only found to be stable on the scale of several hours for potassium. In this work, ab initio calculations were used to shed light on this phenomenon. Decomposition of intermolecular interaction energies of the aza-allyl, aza-enolate, and imine complexes showed that for lithium, the formation of aza-allyl and aza-enolate complexes was driven by electrostatic interactions. For potassium, the dispersion component of the metal interaction with the ligand proved to be more important for the stability of the imine structure. The presence of the imine formation in potassium and partially in sodium was found to be due to the reduced electrostatic nature of these larger metals. The assignment of the experimental NMR spectra was further confirmed with the natural bond order (NBO) analysis as well as the partial charge calculations. Analysis of orbital energies, specifically those of the highest occupied molecular orbitals (HOMOs), as well as the deformation energies of each of the ligands, were also considered. Through these procedures, an understanding of the tendency for each metal to have a unique isomerization pathway was gained.
机译：含有锂，钠和钾的碱金属的最近研究含有锂，钠和钾的allyamides在NMR实验中显示出独特的重排。结果发现锂异构体赞成形成可以存在于溶液中的AZA-烯丙基和AZA-烯醇酯配合物，以进行大量时间。随着金属离子的半径从锂加入钾的范围，亚胺结构的形成偏好是偏好。对于钠，仍然可以隔离亚沙 - 烯丙基络合物，而亚胺结构仅被发现在钾的数小时的稳定性上是稳定的。在这项工作中， AB Initio计算用于阐明这种现象。 AZA-烯丙基，烯丙基和亚胺复合物的分子间相互作用能量的分解表明，对于锂，通过静电相互作用驱动AZA-烯丙基和AZA-烯醇酯配合物的形成。对于钾，与配体的金属相互作用的分散组分证明对亚胺结构的稳定性更为重要。发现亚胺形成的亚胺和部分在钠中的存在是由于这些较大金属的静电性质降低。通过天然键（NBO）分析以及部分电荷计算进一步证实了实验性NMR光谱的分配。还考虑了轨道能量，特别是最高占用的分子轨道（HOMOS）的轨道能量，以及每种配体的变形能量。通过这些程序，获得了对每个金属的趋势进行了解具有独特的异构化途径。

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