Damián Jesús, Rentero Christian, Echeverría Jorge, Mosquera Marta E G
Department of Organic and Inorganic Chemistry, Institute of Chemical Research "Andrés M. del Río" (IQAR), Universidad de Alcalá, Campus Universitario, 28871 Alcalá de Henares, Madrid, Spain.
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Faraday Discuss. 2023 Aug 11;244(0):294-305. doi: 10.1039/d2fd00144f.
Knowing the nature and strength of noncovalent interactions is key to enhancing the synthetic methods and catalytic processes in which they are involved. We present herein the synthesis and characterization of a novel aluminium sodium oximate compound, followed by a comprehensive computational study of the sodium⋯methyl interaction that appears in its crystal structure. Our experimental results have been compared to a large set of structural data retrieved from the Cambridge Structural Database in order to assess the main geometrical preferences of these interactions. Moreover, representative model systems have been studied at the DFT level and the topology of their electron density analysed by means of QTAIM. Although alkali metal⋯methyl short contacts have been traditionally considered as agostic interactions, we have demonstrated here that the physical origin of the attraction relies on the electron-rich carbon atom bound to aluminium and its interaction with the cation.
了解非共价相互作用的性质和强度是改进涉及这些相互作用的合成方法和催化过程的关键。我们在此展示了一种新型肟铝酸钠化合物的合成与表征，随后对其晶体结构中出现的钠⋯甲基相互作用进行了全面的计算研究。我们将实验结果与从剑桥结构数据库检索到的大量结构数据进行了比较，以评估这些相互作用的主要几何偏好。此外，还在密度泛函理论（DFT）水平上研究了代表性的模型体系，并通过量子拓扑原子理论（QTAIM）分析了其电子密度拓扑结构。尽管碱金属⋯甲基短接触传统上被视为 agostic 相互作用，但我们在此证明，这种吸引力的物理起源依赖于与铝相连的富电子碳原子及其与阳离子的相互作用。
