Zheng Qingshu, Borsley Stefan, Nichol Gary S, Duarte Fernanda, Cockroft Scott L
EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, EH9 3FJ, UK.
Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Angew Chem Int Ed Engl. 2019 Sep 2;58(36):12617-12623. doi: 10.1002/anie.201904207. Epub 2019 Aug 2.
Metallophilic interactions are increasingly recognized as playing an important role in molecular assembly, catalysis, and bio-imaging. However, present knowledge of these interactions is largely derived from solid-state structures and gas-phase computational studies rather than quantitative experimental measurements. Here, we have experimentally quantified the role of aurophilic (Au ⋅⋅⋅Au ), platinophilic (Pt ⋅⋅⋅Pt ), palladophilic (Pd ⋅⋅⋅Pd ), and nickelophilic (Ni ⋅⋅⋅Ni ) interactions in self-association and ligand-exchange processes. All of these metallophilic interactions were found to be too weak to be well-expressed in several solvents. Computational energy decomposition analyses supported the experimental finding that metallophilic interactions are overall weak, meaning that favorable dispersion and orbital hybridization contributions from M⋅⋅⋅M binding are largely outcompeted by electrostatic or dispersion interactions involving ligand or solvent molecules. This combined experimental and computational study provides a general understanding of metallophilic interactions and indicates that great care must be taken to avoid over-attributing the energetic significance of metallophilic interactions.
亲金属相互作用在分子组装、催化和生物成像中发挥着重要作用，这一点日益得到认可。然而，目前关于这些相互作用的认识主要来自固态结构和气相计算研究，而非定量实验测量。在此，我们通过实验定量了亲金（Au⋅⋅⋅Au）、亲铂（Pt⋅⋅⋅Pt）、亲钯（Pd⋅⋅⋅Pd）和亲镍（Ni⋅⋅⋅Ni）相互作用在自组装和配体交换过程中的作用。结果发现，所有这些亲金属相互作用都太弱，在几种溶剂中无法很好地表现出来。计算能量分解分析支持了亲金属相互作用总体较弱这一实验发现，这意味着M⋅⋅⋅M键合产生的有利色散和轨道杂化贡献在很大程度上被涉及配体或溶剂分子的静电或色散相互作用所抵消。这项结合实验和计算的研究提供了对亲金属相互作用的全面理解，并表明必须格外小心，避免过度归因于亲金属相互作用的能量意义。
