Metallophilic and Inter‐Ligand Interactions in Diargentous Compounds Bound by a Geometrically Flexible Macrocycle
Metallophilic and Inter‐Ligand Interactions in Diargentous Compounds Bound by a Geometrically Flexible Macrocycle
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DOI：
10.1002/ejic.202300335
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发表时间：
2023-07
影响因子：
2.3
通讯作者：
Qiuran Wang;Michael R. Gau;Brian C. Manor;P. Carroll;N. Tomson
中科院分区：
文献类型：
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作者：
Qiuran Wang;Michael R. Gau;Brian C. Manor;P. Carroll;N. Tomson
报道了一系列由柔性大环配体支撑的单核和双核AgI配合物。配体的几何柔性被发现允许在双银配合物中发生一系列的Ag-−-Ag相互作用，这取决于辅助配体和反离子的身份。对后一种络合物的溶液相动态交换过程的研究发现，通过保持多核性的机制实现了快速的相互转化。用分子中原子的量子理论和基于赫希费尔德配分的独立梯度模型计算了不同几何构型的银心之间的d10-d10相互作用，结果表明，无论银心的相对几何构型如何，Ag-−-Ag相互作用几乎是相同的。相反，两个异氰酸酯单元之间微弱但不可忽略的配体间相互作用可能有助于在固态下观察到折叠配体的几何构型。
A series of mono‐ and di‐nuclear AgIcomplexes supported by a flexible macrocyclic ligand are reported. The geometric flexibility of the ligand was found to allow for a range of Ag−Ag interactions in the disilver complexes, depending on the identities of both the ancillary ligand and the counterion. Studies of the solution‐phase dynamic exchange processes for these latter complexes found rapid interconversion through a mechanism that retained the multi‐nuclearity. Quantum Theory of Atoms in Molecules (QTAIM) and Independent Gradient Model based on Hirshfeld partition (IGMH) analyses are used to evaluate the d10‐d10interactions between silver centers in the various geometries observed for the solid‐state structures of these complexes, revealing nearly identical Ag−Ag interactions, regardless of the relative geometries of the Ag centers. Instead, a weak, but non‐negligible, inter‐ligand interaction between two isocyanide units may contribute to the folded‐ligand geometry observed in the solid state.