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

Abstract

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.

Authors:
; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1991143
Grant/Contract Number:  
SC0001136
Resource Type:
Published Article
Journal Name:
Nature Communications
Additional Journal Information:
Journal Name: Nature Communications Journal Volume: 14 Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Motta, Laura C., and Autschbach, Jochen. Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding. United Kingdom: N. p., 2023. Web. doi:10.1038/s41467-023-39626-8.
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Motta, Laura C., & Autschbach, Jochen. Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding. United Kingdom. https://doi.org/10.1038/s41467-023-39626-8
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Motta, Laura C., and Autschbach, Jochen. Tue . "Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding". United Kingdom. https://doi.org/10.1038/s41467-023-39626-8.
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@article{osti_1991143,
title = {Actinide inverse trans influence versus cooperative pushing from below and multi-center bonding},
author = {Motta, Laura C. and Autschbach, Jochen},
abstractNote = {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.},
doi = {10.1038/s41467-023-39626-8},
journal = {Nature Communications},
number = 1,
volume = 14,
place = {United Kingdom},
year = {Tue Jul 18 00:00:00 EDT 2023},
month = {Tue Jul 18 00:00:00 EDT 2023}
}
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