Tsunoda Mitsukimi, Fleischmann Martin, Jones J Stuart, Bhuvanesh Nattamai, Scheer Manfred, Gabbaï François P
Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, USA.
Institut für Anorganische Chemie, Universität Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany.
Dalton Trans. 2016 Mar 28;45(12):5045-51. doi: 10.1039/c5dt01887k.
As part of our ongoing interest in the supramolecular chemistry of fluorinated organomercurials, we have investigated the interaction of bis(pentafluorophenyl)mercury ((C6F5)2Hg), and trimeric (perfluoro-o-phenylene)mercury ([o-C6F4Hg]3), with nickel(II) N,N'-bis(salicylidene)ethylenediamine) (Ni(salen)). While solution studies monitored by UV-VIS spectroscopy suggest that Ni(salen) interacts with the trinuclear mercury complex in solution, the 1 : 1 adduct (Ni(salen)-(C6F5)2Hg) and the 1 : 1 adducts Ni(salen)-[o-C6F4Hg]3 and [Ni(salen)-[o-C6F4Hg]3-THF-H2O] can be obtained by slow evaporation of solutions containing the two building blocks. While arene-fluoroarene and hydrogen bonding interactions, as well as interactions between mercury and the salen ligand are the predominant forces responsible for the formation of these adducts, Ni(salen)-[o-C6F4Hg]3 and [Ni(salen)-[o-C6F4Hg]3-THF-H2O] also display short Ni-Hg separations consistent with the presence of metallophilic interactions. Quantum theory of atoms in molecules (QTAIM) analyses of the Ni-Hg interactions in these adducts finds that these interactions are dominated by electrostatic and dispersion forces, despite featuring non-negligible covalent contributions.
作为我们对氟化有机汞超分子化学持续关注的一部分，我们研究了双（五氟苯基）汞（（C6F5）2Hg）和三聚（全氟邻亚苯基）汞（[o-C6F4Hg]3）与镍（II）N，N'-双（水杨醛亚胺）乙二胺（Ni（salen））的相互作用。虽然通过紫外-可见光谱监测的溶液研究表明Ni（salen）在溶液中与三核汞配合物相互作用，但通过缓慢蒸发含有这两种构建单元的溶液，可以得到1：1加合物（Ni（salen）-（C6F5）2Hg）以及1：1加合物Ni（salen）-[o-C6F4Hg]3和[Ni（salen）-[o-C6F4Hg]3-THF-H2O]。虽然芳烃-氟芳烃和氢键相互作用，以及汞与salen配体之间的相互作用是形成这些加合物的主要作用力，但Ni（salen）-[o-C6F4Hg]3和[Ni（salen）-[o-C6F4Hg]3-THF-H2O]也显示出短的Ni-Hg间距，这与亲金属相互作用的存在一致。对这些加合物中Ni-Hg相互作用的分子中的原子量子理论（QTAIM）分析发现，尽管这些相互作用具有不可忽略的共价贡献，但它们主要由静电和色散力主导。
