Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides

Straub, Mark D.; Moreau, Liane M.; Qiao, Yusen; Ouellette, Erik T.; Boreen, Michael A.; Lohrey, Trevor D.; Settineri, Nicholas S.; Hohloch, Stephan; Booth, Corwin H.; Minasian, Stefan G.; Arnold, John

doi:10.1021/acs.inorgchem.1c00471

Title: Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides

Journal Article · Mon Apr 12 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c00471· OSTI ID:1779750

^[1]; Moreau, Liane M. ^[2]; Qiao, Yusen ^[2]; Ouellette, Erik T. ^[1];

^[3];

^[4];

^[4]; Booth, Corwin H. ^[2];

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^[3]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States
Univ. of California, Berkeley, CA (United States)

Uranium nitride complexes are attractive targets for chemists as molecular models for the bonding, reactivity, and magnetic properties of next-generation nuclear fuels, but these molecules are uncommon and can be difficult to isolate due to their high reactivity. Here, we describe the synthesis of three new multinuclear uranium nitride complexes, [U(BCMA)₂]₂(μ-N)(μ-κ¹:κ¹-BCMA) (7), [(U(BIMA)₂)₂(μ-N)(μ-NⁱPr)(K₂(μ-η³:η³-CH₂CHNⁱPr)]₂ (8), and [U(BIMA)₂]₂(μ-N)(μ-κ¹:κ¹-BIMA) (9) (BCMA = N,N-bis(cyclohexyl)methylamidinate, BIMA = N,N-bis(iso-propyl)methylamidinate), from U(III) and U(IV) amidinate precursors. By varying the amidinate ligand substituents and azide source, we were able to influence the composition and size of these nitride complexes. ¹⁵N isotopic labeling experiments confirmed the bridging nitride moieties in 7–9 were formed via two-electron reduction of azide. The tetra-uranium cluster 8 was isolated in 99% yield via reductive cleavage of the amidinate ligands; this unusual molecule contains nitrogen-based ligands with formal 1–, 2–, and 3– charges. Additionally, chemical oxidation of the U(IV) precursor U(N₃)(BCMA)₃ yielded the cationic U(V) species [U(N₃)(BCMA)₃][OTf]. Magnetic susceptibility measurements confirmed a U(IV) oxidation state for the uranium centers in the three nitride-bridged complexes and provided a comparison of magnetic behavior in the structurally related U(III)-U(IV)-U(V) series U(BCMA)₃, U(N₃)(BCMA)₃, and [U(N₃)(BCMA)₃][OTf]. At 240 K, the magnetic moments in this series decreased with increasing oxidation state, i.e., U(III) > U(IV) > U(V); this trend follows the decreasing number of 5f valence electrons along this series.

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Research Organization:: Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: NA0003180; NA0000979; AC02-05CH11231; S10-RR027172; S10OD024998

OSTI ID:: 1779750

Alternate ID(s):: OSTI ID: 1856500

Journal Information:: Inorganic Chemistry, Vol. 60, Issue 9; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2050799: Experimental Crystal Structure Determination D., Straub, Mark; M., Moreau, Liane; Yusen, Qiao, https://doi.org/10.5517/ccdc.csd.cc26v0tx The current record is supplemented by this dataset	dataset	January 2021
CCDC 2050801: Experimental Crystal Structure Determination D., Straub, Mark; M., Moreau, Liane; Yusen, Qiao, https://doi.org/10.5517/ccdc.csd.cc26v0wz The current record is supplemented by this dataset	dataset	January 2021
CCDC 2050798: Experimental Crystal Structure Determination D., Straub, Mark; M., Moreau, Liane; Yusen, Qiao, https://doi.org/10.5517/ccdc.csd.cc26v0sw The current record is supplemented by this dataset	dataset	January 2021
CCDC 2050800: Experimental Crystal Structure Determination D., Straub, Mark; M., Moreau, Liane; Yusen, Qiao, https://doi.org/10.5517/ccdc.csd.cc26v0vy The current record is supplemented by this dataset	dataset	January 2021
CCDC 2050797: Experimental Crystal Structure Determination D., Straub, Mark; M., Moreau, Liane; Yusen, Qiao, https://doi.org/10.5517/ccdc.csd.cc26v0rv The current record is supplemented by this dataset	dataset	January 2021
CCDC 2050802: Experimental Crystal Structure Determination D., Straub, Mark; M., Moreau, Liane; Yusen, Qiao, https://doi.org/10.5517/ccdc.csd.cc26v0x0 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2050796: Experimental Crystal Structure Determination D., Straub, Mark; M., Moreau, Liane; Yusen, Qiao, https://doi.org/10.5517/ccdc.csd.cc26v0qt The current record is supplemented by this dataset	dataset	January 2021

Title: Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides

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