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The Energetic Significance of Metallophilic Interactions
Author(s) -
Zheng Qingshu,
Borsley Stefan,
Nichol Gary S.,
Duarte Fernanda,
Cockroft Scott L.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201904207
Subject(s) - chemistry , molecule , chemical physics , computational chemistry , fragment molecular orbital , interaction energy , non covalent interactions , ligand (biochemistry) , dispersion (optics) , orbital hybridisation , molecular orbital , physics , hydrogen bond , molecular orbital theory , quantum mechanics , receptor , biochemistry , organic chemistry
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 I ⋅⋅⋅Au I ), platinophilic (Pt II ⋅⋅⋅Pt II ), palladophilic (Pd II ⋅⋅⋅Pd II ), and nickelophilic (Ni II ⋅⋅⋅Ni II ) 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.