Tetrahedral 4c-2e and Trigonal-Bipyramidal 5c-2e Bonds in Actinide-Containing Clusters with Quasi-Lewis Structures Identified via an Orbital Alignment and Localization Scheme.

The study of metal-metal bonding, particularly in heterometallic clusters containing actinide elements, is a fascinating area of research due to its material and catalytic properties. However, understanding the complex bonding within these clusters poses challenges for traditional bonding analysis tools. The fragile bonding capability of actinide elements and the complicated orbital mixing of metal-metal and metal-ligand bonding interactions prevent the discovery of novel actinide-metal bonds and the precise bonding description of these clusters in terms of traditional Lewis structures. To address these issues, we introduced a novel orbital alignment and localization scheme, which helps separate the two above-mentioned bonding interactions. Herein, we employed the scheme to analyze two multinuclear actinide clusters containing U2Ni2 and U2Ni3 metal frameworks. Through the bonding analysis, we obtained a set of pure metallic localized molecular orbitals, which provide chemically intuitive bonding/nonbonding information. By observing these orbitals, we discovered a remarkable tetrahedral four-center two-electron σ bond and a unique trigonal-bipyramidal five-center two-electron σ bond for the U2Ni2 and U2Ni3 clusters, respectively. Furthermore, we were able to put forward quasi-Lewis structure descriptions for the two clusters, elucidating their metal-metal bonds, molecular structures, stability, and magnetic properties, successfully expanding the applicability of Lewis structures to the actinide clusters.

• Publication year

  2025

• Venue

  Inorganic Chemistry

• Publication date

  2025-11-12

• Fields of study

  Medicine, Materials Science, Chemistry

• Identifiers
  DOI 10.1021/acs.inorgchem.5c04106PMID 41229144
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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