Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides
Abstract
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,more »
- Authors:
-
[1];
[3];
[3];
[4];
[4];
[2];
[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)
- Publication Date:
- Research Org.:
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- 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
- OSTI Identifier:
- 1779750
- Alternate Identifier(s):
- OSTI ID: 1856500
- Grant/Contract Number:
- NA0003180; NA0000979; AC02-05CH11231; S10-RR027172; S10OD024998
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 60; Journal Issue: 9; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Uranium; nitride; actinide; amidinate; uranium
Citation Formats
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., and Arnold, John. Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides. United States: N. p., 2021.
Web. doi:10.1021/acs.inorgchem.1c00471.
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. Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides. United States. https://doi.org/10.1021/acs.inorgchem.1c00471
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., and Arnold, John. Mon .
"Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides". United States. https://doi.org/10.1021/acs.inorgchem.1c00471. https://www.osti.gov/servlets/purl/1779750.
@article{osti_1779750,
title = {Amidinate Supporting Ligands Influence Molecularity in Formation of Uranium Nitrides},
author = {Straub, Mark D. and Moreau, Liane M. and Qiao, Yusen and Ouellette, Erik T. and Boreen, Michael A. and Lohrey, Trevor D. and Settineri, Nicholas S. and Hohloch, Stephan and Booth, Corwin H. and Minasian, Stefan G. and Arnold, John},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.1c00471},
journal = {Inorganic Chemistry},
number = 9,
volume = 60,
place = {United States},
year = {Mon Apr 12 00:00:00 EDT 2021},
month = {Mon Apr 12 00:00:00 EDT 2021}
}
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