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DOE OSTI · 3024189

Synthesis and Computational Analysis of Uranium(III)-Pnictogen Bonds

Lopez, Lauren M. [Purdue University, West Lafayette, IN (United States)]·Perales, Diana [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000168859856)·Smolek, Allison N. [Purdue University, West Lafayette, IN (United States)]·Zeller, Matthias [Purdue University, West Lafayette, IN (United States)] (ORCID:000000023305852X)·Vlaisavljevich, Bess [University of Iowa, Iowa City, IA (United States)] (ORCID:0000000160650732)·Bart, Suzanne C. [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000289189051)
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Abstract

In this report, we describe the synthesis and characterization of two novel complexes that contain uranium(III)-pnictogen (P: 1-PMes 2 ; As: 1-AsMes 2 ) bonds to elucidate the degrees of covalency among these bonds. To our knowledge, this is the first reported uranium(III)-arsenic complex to be synthesized and characterized. Analysis of the phosphorus and arsenic bonds reveals a similar electronic environment, assessed by UV–vis NIR, that is comparable to other previously reported uranium(III) complexes. A computational analysis of these compounds and their congeners, N, Sb, and Bi, was performed to identify trends in the overall bonding character of the complexes. This analysis shows that bond covalency decreases as the pnictogen becomes heavier and that overall the interaction energy and its components decrease down the group. Here, this study provides an in-depth analysis and understanding of the nature of bonding between hard actinide and soft pnictogen centers.

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ActinidesCovalent bondingNuclear magnetic resonance spectroscopyPnictidesUranium

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BibTeXRIS

Lopez, Lauren M. [Purdue University, West Lafayette, IN (United States)], Perales, Diana [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000168859856), Smolek, Allison N. [Purdue University, West Lafayette, IN (United States)], Zeller, Matthias [Purdue University, West Lafayette, IN (United States)] (ORCID:000000023305852X), Vlaisavljevich, Bess [University of Iowa, Iowa City, IA (United States)] (ORCID:0000000160650732), Bart, Suzanne C. [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000289189051). 2026-01-13. Synthesis and Computational Analysis of Uranium(III)-Pnictogen Bonds. https://doi.org/10.1021/jacs.5c19802

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