Role of Dispersion in Metallophilic Hg•••M Interactions (M = Cu, Ag, Au) within Coinage Metal Complexes of Bis(6-diphenylphosphinoacenaphth-5-yI)mercury
Role of Dispersion in Metallophilic Hg•••M Interactions (M = Cu, Ag, Au) within Coinage Metal Complexes of Bis(6-diphenylphosphinoacenaphth-5-yI)mercury
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DOI：
10.1021/acs.inorgchem.6b02056
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发表时间：
2016-11-07
影响因子：
4.6
通讯作者：
Beckmann, Jens
中科院分区：
文献类型：
--
作者：
Hupf, Emanuel;Kather, Ralf;Beckmann, Jens
以双（6-二苯基膦基苊-5-基）汞（1）为配体，合成了1个中心点CuCl和[1个中心点Cu（NCMe）] BF 4铜（I）配合物，并用多核NMR和X射线晶体学对其进行了表征。DFT计算采用AIM和ELI-D空间划分方案内的电子和电子对密度的拓扑分析揭示了显着的亲金属Hg中心点Cu相互作用。根据非共价相互作用（NCI）指数对非共价键结合方面的评价不仅适用于Cu络合物1中心点CuCl和[1中心点Cu（NCMe）] BF 4，而且适用于先前报道的Ag和Au络合物，即[1中心点MCl]。（M = Ag，Au）和[1个中心点M（NCMe）（+）]（M = Ag，n = 2; M = Au，n = 0），并且促进了吸引分散Hg中心点M相互作用的分配，其中Hg中心点Cu接触与Hg中心点Ag相当但弱于Hg中心点Au相互作用。吸引性非共价键区域的局部化按Cu < Ag < Au的顺序增加。
The previously reported bis(6-diphenylphosphinoacenaphth-5-yl)mercury (1) was used as ligand for the preparation of the copper(I) complexes, 1 center dot CuCl and [1 center dot Cu(NCMe)]BF4, which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations employing topological analysis of the electron and electron pair densities within the AIM and ELI-D space-partitioning schemes revealed significant metallophilic Hg center dot center dot center dot Cu interactions. Evaluation of noncovalent bonding aspects according to the noncovalent interaction (NCI) index was applied not only for the Cu complexes 1 center dot CuCl and [1 center dot Cu(NCMe)]BF4 but also for the previously reported Ag and Au complexes, namely, [1 center dot MCl] (M = Ag, Au) and [1 center dot M(NCMe)(+) (M = Ag, n = 2; M = Au, n = 0), and facilitated the assignment of attractive dispersive Hg center dot center dot center dot M interactions with the Hg center dot center dot center dot Cu contacts being comparable to the Hg center dot center dot center dot Ag but weaker than the Hg center dot center dot center dot Au interactions. The localization of the attractive noncovalent bonding regions increases in the order Cu < Ag < Au.