Abstract
AbstractActinide-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.
Funder
U.S. Department of Energy
Publisher
Springer Science and Business Media LLC
Subject
General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry,Multidisciplinary
Cited by
3 articles.
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