Hupf Emanuel, Kather Ralf, Vogt Matthias, Lork Enno, Mebs Stefan, Beckmann Jens
Institut für Anorganische Chemie und Kristallographie, Universität Bremen , Leobener Strasse, 28359 Bremen, Germany.
Institut für Experimentalphysik, Freie Universität Berlin , Arnimallee 14, 14195 Berlin, Germany.
Inorg Chem. 2016 Nov 7;55(21):11513-11521. doi: 10.1021/acs.inorgchem.6b02056. Epub 2016 Oct 17.
The previously reported bis(6-diphenylphosphinoacenaphth-5-yl)mercury (1) was used as ligand for the preparation of the copper(I) complexes, 1·CuCl and [1·Cu(NCMe)]BF, 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···Cu interactions. Evaluation of noncovalent bonding aspects according to the noncovalent interaction (NCI) index was applied not only for the Cu complexes 1·CuCl and [1·Cu(NCMe)]BF but also for the previously reported Ag and Au complexes, namely, [1·MCl] (M = Ag, Au) and [1·M(NCMe)] (M = Ag, n = 2; M = Au, n = 0), and facilitated the assignment of attractive dispersive Hg···M interactions with the Hg···Cu contacts being comparable to the Hg···Ag but weaker than the Hg···Au interactions. The localization of the attractive noncovalent bonding regions increases in the order Cu < Ag < Au.
先前报道的双（6-二苯基膦基苊烯-5-基）汞（1）用作配体来制备铜（I）配合物1·CuCl和[1·Cu（NCMe）]BF，通过多核核磁共振光谱和X射线晶体学对其进行了表征。采用AIM和ELI-D空间划分方案内电子和电子对密度拓扑分析的密度泛函理论计算揭示了显著的亲金属Hg···Cu相互作用。根据非共价相互作用（NCI）指数对非共价键合方面的评估不仅应用于铜配合物1·CuCl和[1·Cu（NCMe）]BF，还应用于先前报道的银和金配合物，即[1·MCl]（M = Ag，Au）和[1·M（NCMe）]（M = Ag，n = 2；M = Au，n = 0），并有助于确定有吸引力的色散Hg···M相互作用，其中Hg···Cu接触与Hg···Ag相当，但比Hg···Au相互作用弱。有吸引力的非共价键合区域的定位按Cu < Ag < Au的顺序增加。
