Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding

Actinide-ligand bonds with high multiplicities remain poorly understood. Decades ago, an effect known as 6p pushing from below (PFB) was proposed to enhance actinide covalency. A related effect—also poorly understood—is inverse trans influence (ITI). The present computational study of actinide-ligan...

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Bibliographic Details
Published in:Nature communications 2023-07, Vol.14 (1), p.4307-4307, Article 4307
Main Authors: Motta, Laura C., Autschbach, Jochen
Format: Article
Language:English
Subjects:
639/638/263/910
639/638/563/606
639/638/563/979
Chemical bonds
Covalence
Electrostatic properties
Humanities and Social Sciences
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ligands
multidisciplinary
Pushing
Science
Science (multidisciplinary)
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Summary:Actinide-ligand bonds with high multiplicities remain poorly understood. Decades ago, an effect known as 6p pushing from below (PFB) was proposed to enhance actinide covalency. A related effect—also poorly understood—is inverse trans influence (ITI). The present computational study of actinide-ligand covalent interactions with high bond multiplicities quantifies the energetic contributions from PFB and identifies a hitherto overlooked fourth bonding interaction for 2nd-row ligands in the studied organometallic systems. The latter are best described by a terminal O/N ligand exhibiting quadruple bonding interactions with the actinide. The 4th interaction may be characterized as a multi-center or charge-shift bond involving the trans ligand. It is shown in this work that the 4th bonding interaction is a manifestation of ITI, assisted by PFB, and provides a long-sought missing piece in the understanding of actinide chemistry. Actinide-ligand bonds with high multiplicities remain poorly understood. Here, the authors investigate covalency in actinide complexes and identify terminal O and N ligands that are triply to quadruply bonded to the actinide, facilitated by electrostatic, steric, and covalent interactions.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-023-39626-8