On the origin of low-valent uranium oxidation state.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
10 Aug 2024
10 Aug 2024
Historique:
received:
05
12
2023
accepted:
24
07
2024
medline:
11
8
2024
pubmed:
11
8
2024
entrez:
10
8
2024
Statut:
epublish
Résumé
The significant interest in actinide bonding has recently focused on novel compounds with exotic oxidation states. However, the difficulty in obtaining relevant high-quality experimental data, particularly for low-valent actinide compounds, prevents a deeper understanding of 5f systems. Here we show X-ray absorption near-edge structure (XANES) measurements in the high-energy resolution fluorescence detection (HERFD) mode at the uranium M
Identifiants
pubmed: 39127780
doi: 10.1038/s41467-024-50924-7
pii: 10.1038/s41467-024-50924-7
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
6861Subventions
Organisme : EC | EU Framework Programme for Research and Innovation H2020 | H2020 Priority Excellent Science | H2020 European Research Council (H2020 Excellent Science - European Research Council)
ID : 759696
Informations de copyright
© 2024. The Author(s).
Références
Boronski, J. T. et al. A crystalline tri-thorium cluster with σ-aromatic metal–metal bonding. Nature 598, 72–75 (2021).
pubmed: 34425584
doi: 10.1038/s41586-021-03888-3
MacDonald, M. R. et al. Identification of the +2 oxidation state for uranium in a crystalline molecular complex, [K(2.2.2-Cryptand)][(C
pubmed: 23984753
doi: 10.1021/ja406791t
La Pierre, H. S., Kameo, H., Halter, D. P., Heinemann, F. W. & Meyer, K. Coordination and redox isomerization in the reduction of a uranium(III) monoarene complex. Angew. Chem. Int. Ed. 53, 7154–7157 (2014).
doi: 10.1002/anie.201402048
Wooles, A. J. et al. Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings. Nat. Commun. 9, 2097 (2018).
pubmed: 29844376
pmcid: 5974406
doi: 10.1038/s41467-018-04560-7
Barluzzi, L., Giblin, S. R., Mansikkamäki, A. & Layfield, R. A. Identification of oxidation state +1 in a molecular uranium complex. J. Am. Chem. Soc. 144, 18229–18233 (2022).
pubmed: 36169550
pmcid: 9562434
doi: 10.1021/jacs.2c06519
Dutkiewicz, M. S. et al. Organometallic neptunium(III) complexes. Nat. Chem. 8, 797–802 (2016).
pubmed: 27442286
doi: 10.1038/nchem.2520
Kvashnina, K. O. et al. A novel metastable pentavalent plutonium solid phase on the pathway from aqueous plutonium(VI) to PuO2 nanoparticles. Angew. Chem. Int. Ed. 58, 17558–17562 (2019).
doi: 10.1002/anie.201911637
Cary, S. K. et al. Incipient class II mixed valency in a plutonium solid-state compound. Nat. Chem. 9, 856–861 (2017).
pubmed: 28837172
doi: 10.1038/nchem.2777
Gaiser, A. N. et al. Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes. Nat. Commun. 12, 7230 (2021).
pubmed: 34893651
pmcid: 8664847
doi: 10.1038/s41467-021-27576-y
Polinski, M. J. et al. Unusual structure, bonding and properties in a californium borate. Nat. Chem. 6, 387–392 (2014).
pubmed: 24755589
doi: 10.1038/nchem.1896
Carter, K. P. et al. Structural and spectroscopic characterization of an einsteinium complex. Nature 590, 85–88 (2021).
pubmed: 33536647
doi: 10.1038/s41586-020-03179-3
Avens, L. R. et al. A convenient entry into trivalent actinide chemistry: synthesis and characterization of AnI3(THF)4 and An[N(SiMe3)2]3 (An = U, Np, Pu). Inorg. Chem. 33, 2248–2256 (1994).
doi: 10.1021/ic00088a030
Keener, M. et al. Multielectron redox chemistry of uranium by accessing the +II oxidation state and enabling reduction to a U(I) synthon. J. Am. Chem. Soc. 145, 16271–16283 (2023).
pubmed: 37440295
doi: 10.1021/jacs.3c05626
Boreen, M. A. et al. A uranium tri-rhenium triple inverse. Sandwich Compound. J. Am. Chem. Soc. 141, 5144–5148 (2019).
pubmed: 30892880
doi: 10.1021/jacs.9b01331
Kvashnina, K. O., Butorin, S. M., Martin, P. & Glatzel, P. Chemical state of complex uranium oxides. Phys. Rev. Lett. 111, 253002 (2013).
pubmed: 24483742
doi: 10.1103/PhysRevLett.111.253002
Kvashnina, K. O., Kvashnin, Y. O. & Butorin, S. M. Role of resonant inelastic X-ray scattering in high-resolution core-level spectroscopy of actinide materials. J. Electron. Spectrosc. Relat. Phenom. 194, 27–36 (2014).
doi: 10.1016/j.elspec.2014.01.016
Leinders, G., Bes, R., Pakarinen, J., Kvashnina, K. & Verwerft, M. Evolution of the uranium chemical state in mixed-valence oxides. Inorg. Chem. 56, 6784–6787 (2017).
pubmed: 28590135
doi: 10.1021/acs.inorgchem.7b01001
Kvashnina, K. O. & Butorin, S. M. High-energy resolution X-ray spectroscopy at actinide M
doi: 10.1039/D1CC04851A
Caciuffo, R. & Lander, G. H. X-ray synchrotron radiation studies of actinide materials. J. Synchrotron Radiat. 28, 1692–1708 (2021).
pubmed: 34738923
pmcid: 8570219
doi: 10.1107/S1600577521009413
Kvashnina, K. O. & Scheinost, A. C. A Johann-type X-ray emission spectrometer at the Rossendorf beamline. J. Synchrotron Radiat. 23, 836–841 (2016).
pubmed: 27140166
doi: 10.1107/S1600577516004483
Vitova, T. et al. Polarization dependent high energy resolution X-ray absorption study of dicesium uranyl tetrachloride. Inorg. Chem. 54, 174–182 (2015).
pubmed: 25485552
doi: 10.1021/ic5020016
Bès, R. et al. Use of HERFD–XANES at the U L
pubmed: 27132487
doi: 10.1021/acs.inorgchem.6b00014
Hunault, M. O. J. Y. et al. Speciation change of uranyl in lithium borate glasses. Inorg. Chem. 58, 6858–6865 (2019).
pubmed: 31025856
doi: 10.1021/acs.inorgchem.9b00305
Gerber, E. et al. To form or not to form: PuO2 nanoparticles at acidic pH. Environ. Sci. Nano 9, 1509–1518 (2022).
pubmed: 35520632
pmcid: 9009106
doi: 10.1039/D1EN00666E
Minasian, S. G. et al. Determining relative f and d orbital contributions to M–Cl covalency in MCl
pubmed: 22404133
doi: 10.1021/ja2105015
Su, J. et al. Energy-degeneracy-driven covalency in actinide bonding. J. Am. Chem. Soc. 140, 17977–17984 (2018).
pubmed: 30540455
doi: 10.1021/jacs.8b09436
Sergentu, D.-C. & Autschbach, J. Covalency in actinide(IV) hexachlorides in relation to the chlorine K-edge X-ray absorption structure. Chem. Sci. 13, 3194–3207 (2022).
pubmed: 35414875
pmcid: 8926251
doi: 10.1039/D1SC06454A
Thibaut, E., Boutique, J. P., Verbist, J. J., Levet, J. C. & Noel, H. Electronic structure of uranium halides and oxyhalides in the solid state. An X-ray photoelectron spectral study of bonding ionicity. J. Am. Chem. Soc. 104, 5266–5273 (1982).
doi: 10.1021/ja00384a002
Ilton, E. S. & Bagus, P. S. XPS determination of uranium oxidation states. Surf. Interface Anal. 43, 1549–1560 (2011).
doi: 10.1002/sia.3836
Neidig, M. L., Clark, D. L. & Martin, R. L. Covalency in f-element complexes. Coord. Chem. Rev. 257, 394–406 (2013).
doi: 10.1016/j.ccr.2012.04.029
Beekmeyer, R. & Kerridge, A. Assessing covalency in cerium and uranium hexachlorides: a correlated wavefunction and density functional theory study. Inorganics 3, 482–499 (2015).
doi: 10.3390/inorganics3040482
Gianopoulos, C. G. et al. Bonding in uranium(V) hexafluoride based on the experimental electron density distribution measured at 20 K. Inorg. Chem. 56, 1775–1778 (2017).
pubmed: 28165229
doi: 10.1021/acs.inorgchem.6b02971
Tanti, J., Lincoln, M. & Kerridge, A. Decomposition of d- and f-shell contributions to uranium bonding from the quantum theory of atoms in molecules: application to uranium and uranyl halides. Inorganics 6, 88 (2018).
Gibson, J. K. Bond dissociation energies reveal the participation of d electrons in f-element halide bonding. J. Phys. Chem. A 126, 272–285 (2022).
pubmed: 35007073
doi: 10.1021/acs.jpca.1c09090
Butorin, S. M. et al. Chemical reduction of actinides probed by resonant inelastic X-ray scattering. Anal. Chem. 85, 11196–11200 (2013).
pubmed: 24187957
doi: 10.1021/ac4020534
Booth, C. H. et al. Delocalization and occupancy effects of 5f orbitals in plutonium intermetallics using L3-edge resonant X-ray emission spectroscopy. J. Electron Spectrosc. Relat. Phenom. 194, 57–65 (2014).
doi: 10.1016/j.elspec.2014.03.004
Kvashnina, K. O. et al. Sensitivity to actinide doping of uranium compounds by resonant inelastic X-ray scattering at uranium L
pubmed: 26255719
doi: 10.1021/acs.analchem.5b01699
Butorin, S. M., Modin, A., Vegelius, J. R., Kvashnina, K. O. & Shuh, D. K. Probing chemical bonding in uranium dioxide by means of high-resolution X-ray absorption spectroscopy. J. Phys. Chem. C 120, 29397–29404 (2016).
doi: 10.1021/acs.jpcc.6b09335
Ramanantoanina, H., Kuri, G., Daul, C. & Bertsch, J. Core electron excitations in U4+: modelling of the: N d105f2 → n d95f3 transitions with n = 3, 4 and 5 by ligand field tools and density functional theory. Phys. Chem. Chem. Phys. 18, 19020–19031 (2016).
pubmed: 27356168
doi: 10.1039/C6CP01395C
Booth, C. H. et al. Probing 5f-state configurations in URu
doi: 10.1103/PhysRevB.94.045121
Kvashnina, K. O., Walker, H. C., Magnani, N., Lander, G. H. & Caciuffo, R. Resonant X-ray spectroscopy of uranium intermetallics at the M 4, 5 edges of uranium. Phys. Rev. B 95, 245103 (2017).
doi: 10.1103/PhysRevB.95.245103
Amidani, L. et al. Understanding the size effects on the electronic structure of ThO2 nanoparticles. Phys. Chem. Chem. Phys. 21, 10635–10643 (2019).
pubmed: 31080986
doi: 10.1039/C9CP01283D
Butorin, S. M. 3d-4f resonant inelastic X-ray scattering of actinide dioxides: crystal-field multiplet description. Inorg. Chem. 59, 16251–16264 (2020).
pubmed: 33136396
pmcid: 7672702
doi: 10.1021/acs.inorgchem.0c02032
Amidani, L. et al. Probing the local coordination of hexavalent uranium and the splitting of 5f orbitals induced by chemical bonding. Inorg. Chem. 60, 16286–16293 (2021).
pubmed: 34677932
doi: 10.1021/acs.inorgchem.1c02107
Bagus, P. S., Schacherl, B. & Vitova, T. Computational and spectroscopic tools for the detection of bond covalency in Pu(IV) materials. Inorg. Chem. 60, 16090–16102 (2021).
pubmed: 34634201
pmcid: 8564760
doi: 10.1021/acs.inorgchem.1c01331
Polly, R., Schacherl, B., Rothe, J. & Vitova, T. Relativistic multiconfigurational Ab initio calculation of uranyl 3d4f resonant inelastic X-ray scattering. Inorg. Chem. 60, 18764–18776 (2021).
pubmed: 34818001
pmcid: 8693175
doi: 10.1021/acs.inorgchem.1c02364
Lander, G. H. et al. Resonant inelastic X-ray spectroscopy on UO
pubmed: 33325375
doi: 10.1088/1361-648X/abc4d2
Butorin, S. M. Advanced X-ray spectroscopy of actinide trichlorides. J. Chem. Phys. 155, 164103 (2021).
pubmed: 34717360
doi: 10.1063/5.0062927
Sergentu, D.-C. & Autschbach, J. X-ray absorption spectra of f-element complexes: insight from relativistic multiconfigurational wavefunction theory. Dalton Trans. 51, 1754–1764 (2022).
pubmed: 35022645
doi: 10.1039/D1DT04075H
Marino, A. et al. Singlet magnetism in intermetallic UGa 2 unveiled by inelastic X-ray scattering. Phys. Rev. B 108, 045142 (2023).
doi: 10.1103/PhysRevB.108.045142
Ehrman, J. N. et al. Unveiling hidden shake-up features in the uranyl M4-edge spectrum. JACS Au 4, 1134–1141 (2024).
pubmed: 38559711
pmcid: 10976573
doi: 10.1021/jacsau.3c00838
Stanistreet-Welsh, K. & Kerridge, A. Bounding [AnO
pubmed: 37615175
doi: 10.1039/D3CP03149G
de Groot, F. & Kotani, A. Core Level Spectroscopy of Solids. (CRC Press, Boca Raton, 2008).
Haverkort, M. W., Zwierzycki, M. & Andersen, O. K. Multiplet ligand-field theory using Wannier orbitals. Phys. Rev. B Condens. Matter Mater. Phys. 85, 165113 (2012).
Koepernik, K. & Eschrig, H. Full-potential nonorthogonal local-orbital minimum-basis band-structure scheme. Phys. Rev. B 59, 1743–1757 (1999).
doi: 10.1103/PhysRevB.59.1743
Bader, R. F. W. Atoms in Molecules: A Quantum Theory. 22 (Clarendon Press, 1994).
Kerridge, A. Quantification of f-element covalency through analysis of the electron density: insights from simulation. Chem. Commun. 53, 6685–6695 (2017).
doi: 10.1039/C7CC00962C
Scheinost, A. C. et al. ROBL-II at ESRF: a synchrotron toolbox for actinide research. J. Synchrotron Radiat. 28, 333–349 (2021).
pubmed: 33399586
pmcid: 7842221
doi: 10.1107/S1600577520014265
Retegan, M. Crispy: v0.7.4. https://doi.org/10.5281/zenodo.1008184%7D (2019).
Otero-de-la-Roza, A., Johnson, E. R. & Luaña, V. Critic2: A program for real-space analysis of quantum chemical interactions in solids. Comput. Phys. Commun. 185, 1007–1018 (2014).
doi: 10.1016/j.cpc.2013.10.026
Neese, F. Software update: the ORCA program system—version 5.0. WIREs Comput. Mol. Sci. 12, e1606 (2022).
doi: 10.1002/wcms.1606
Scheibe, B. et al. UF4 and the high-pressure polymorph HP-UF4. Chem. Eur. J. 25, 7366–7374 (2019).
pubmed: 30912599
doi: 10.1002/chem.201900639
Rudel, S. S. & Kraus, F. Facile syntheses of pure uranium halides: UCl
pubmed: 28429019
doi: 10.1039/C7DT00726D
Rudel, S. S., Deubner, H. L., Scheibe, B., Conrad, M. & Kraus, F. Facile syntheses of pure uranium(III) halides: UF3, UCl3, UBr3, and UI3. Z. Für Anorg. Allg. Chem. 644, 323–329 (2018).
doi: 10.1002/zaac.201700402
Larson, A. C., Roof, R. B. & Cromer, D. T. The crystal structure of UF4. Acta Crystallogr. 17, 555–UF558 (1964).
doi: 10.1107/S0365110X64001293
Taylor, J. C. & Wilson, P. W. Crystal structure of uranium tetrabromide by X-ray and neutron diffraction. Acta Crystallogr. Sect. B 30, 2664–2667 (1974).
doi: 10.1107/S0567740874007758
Levy, J. H., Taylor, J. C. & Waugh, A. B. Crystal structure of uranium(IV) tetraiodide by X-ray and neutron diffraction. Inorg. Chem. 19, 672–674 (1980).
doi: 10.1021/ic50205a019
Schleid, T., Meyer, G. & Morss, L. R. Facile synthesis of UCl
doi: 10.1016/0022-5088(87)90175-5
Levy, J. H., Taylor, J. C. & Wilson, P. W. The structure of uranium tribromide by neutron diffraction profile analysis. J. Less Common Met. 39, 265–270 (1975).
doi: 10.1016/0022-5088(75)90200-3
Murasik, A., Fischer, P. & Szczepaniak, W. Neutron diffraction study of long-range antiferromagnetic order and crystal structure of uranium (III) tri-iodide. J. Phys. C Solid State Phys. 14, 1847 (1981).
doi: 10.1088/0022-3719/14/13/009