The Energetic Significance of Metallophilic Interactions.
The Energetic Significance of Metallophilic Interactions.
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DOI：
10.1002/anie.201904207
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发表时间：
2019-08
影响因子：
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通讯作者：
Qingshu Zheng;Stefan Borsley;G. Nichol;F. Duarte;S. Cockroft
中科院分区：
文献类型：
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作者：
Qingshu Zheng;Stefan Borsley;G. Nichol;F. Duarte;S. Cockroft
亲金属相互作用在分子组装、催化和生物成像等领域发挥着重要作用。然而，目前的知识，这些相互作用主要是来自固态结构和气相计算研究，而不是定量的实验测量。在这里，我们已经通过实验量化了亲金（AuI···AuI），亲铂（PtII···PtII），亲钯（PdII···PdII）和亲镍（NiII···NiII）相互作用在自缔合和配体交换过程中的作用。发现所有这些亲金属相互作用太弱，无法在几种不同溶剂中良好表达。计算能量分解分析支持亲金属相互作用总体较弱的实验发现，这意味着M···M结合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超越。这种结合实验和计算的研究提供了一个一般性的理解，亲金属相互作用，并表明，必须非常小心，以避免过度归因于亲金属相互作用的能量意义。
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 (AuI···AuI), platinophilic (PtII···PtII), palladophilic (PdII···PdII) and nickelophilic (NiII···NiII) 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 different 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.