Group 11 m-Terphenyl Complexes Featuring Metallophilic Interactions.
Group 11 m-Terphenyl Complexes Featuring Metallophilic Interactions.
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DOI：
10.1021/acs.inorgchem.0c03623
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发表时间：
2021-07
影响因子：
4.6
通讯作者：
Yu Liu;Laurence J. Taylor;S. Argent;J. McMaster;D. Kays
中科院分区：
文献类型：
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作者：
Yu Liu;Laurence J. Taylor;S. Argent;J. McMaster;D. Kays
以铁（II）配合物（2，6-Mes_2C_6H_3）_2Fe和（2，6-Xyl_2C_6H_3）_2Fe（Mes = 2，4，6-Me_3C_6H_2; Xyl = 2，6-Me_2C_6H_3）为原料，通过复分解反应合成了一系列11族间三联苯配合物。[2，6-Mes 2C 6 H3 M]2（1，M = Cu; 2，M = Ag; 6，M = Au）和[2，6-Xyl 2C 6 H3 M]2（3，M = Cu; 4，M = Ag）在固态下是二聚体，尽管根据配体观察到不同的几何形状。这些配合物的特点是金属-金属距离短，在预期范围内的亲金属相互作用。虽然使用该复分解途径容易分离1-4，但是金络合物6在环境温度下在溶液中不稳定，并且仅以低产率从（2，6-Mes 2C 6 H3）Au·SMe 2（5）的分解获得。NMR光谱测量，包括扩散有序光谱，表明1-4在苯-d 6溶液中保持二聚体。金属-金属的相互作用已被检查计算使用原子在分子中的量子理论和能量分解分析采用自然轨道的化学价。
A series of group 11 m-terphenyl complexes have been synthesized via a metathesis reaction from the iron(II) complexes (2,6-Mes2C6H3)2Fe and (2,6-Xyl2C6H3)2Fe (Mes = 2,4,6-Me3C6H2; Xyl = 2,6-Me2C6H3). [2,6-Mes2C6H3M]2 (1, M = Cu; 2, M = Ag; 6, M = Au) and [2,6-Xyl2C6H3M]2 (3, M = Cu; 4, M = Ag) are dimeric in the solid state, although different geometries are observed depending on the ligand. These complexes feature short metal-metal distances in the expected range for metallophilic interactions. While 1-4 are readily isolated using this metathetical route, the gold complex 6 is unstable in solution at ambient temperatures and has only been obtained in low yield from the decomposition of (2,6-Mes2C6H3)Au·SMe2 (5). NMR spectroscopic measurements, including diffusion-ordered spectroscopy, suggest that 1-4 remain dimeric in a benzene-d6 solution. The metal-metal interactions have been examined computationally using the Quantum Theory of Atoms in Molecules and by an energy decomposition analysis employing natural orbitals for chemical valence.