The Energetic Significance of Metallophilic Interactions.

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ID: 2280
2019
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Ranked #50 of 192 articles by views in angewandte chemie (international ed in english)

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Abstract
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.
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zheng2019theangewandte Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Zheng, Qingshu;Borsley, Stefan;Nichol, Gary S;Duarte, Fernanda;Cockroft, Scott Lee;
Journal angewandte chemie (international ed in english)
Year 2019
DOI
10.1002/anie.201904207
URL
Keywords Keywords not found

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