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

Motta, Laura C.; Autschbach, Jochen

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

dc.contributor.author	Motta, Laura C.
dc.contributor.author	Autschbach, Jochen
dc.date.accessioned	2024-07-11T14:38:00Z
dc.date.available	2024-07-11T14:38:00Z
dc.date.issued	2023-07-18
dc.description	© The Author(s), 2023. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Motta, L. C., & Autschbach, J. (2023). Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding. Nature Communications, 14(1), 4307, https://doi.org/10.1038/s41467-023-39626-8.
dc.description.abstract	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.
dc.description.sponsorship	Supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program, under grant DE-SC0001136 to J.A.
dc.identifier.citation	Motta, L. C., & Autschbach, J. (2023). Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding. Nature Communications, 14(1), 4307.
dc.identifier.doi	10.1038/s41467-023-39626-8
dc.identifier.uri	https://hdl.handle.net/1912/69729
dc.publisher	Nature Research
dc.relation.uri	https://doi.org/10.1038/s41467-023-39626-8
dc.rights	Attribution 4.0 International
dc.rights.uri	http://creativecommons.org/licenses/by/4.0/
dc.subject	Chemical Bonding
dc.subject	Computational Chemistry
dc.subject	Density functional theory
dc.title	Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding
dc.type	Article
dspace.entity.type	Publication
relation.isAuthorOfPublication	72faab15-e8c5-4575-8397-6f260571f1a2
relation.isAuthorOfPublication.latestForDiscovery	72faab15-e8c5-4575-8397-6f260571f1a2