Isolation and characterization of a californium metallocene.
Journal
Nature
ISSN: 1476-4687
Titre abrégé: Nature
Pays: England
ID NLM: 0410462
Informations de publication
Date de publication:
11 2021
11 2021
Historique:
received:
15
04
2021
accepted:
15
09
2021
entrez:
18
11
2021
pubmed:
19
11
2021
medline:
19
11
2021
Statut:
ppublish
Résumé
Californium (Cf) is currently the heaviest element accessible above microgram quantities. Cf isotopes impose severe experimental challenges due to their scarcity and radiological hazards. Consequently, chemical secrets ranging from the accessibility of 5f/6d valence orbitals to engage in bonding, the role of spin-orbit coupling in electronic structure, and reactivity patterns compared to other f elements, remain locked. Organometallic molecules were foundational in elucidating periodicity and bonding trends across the periodic table
Identifiants
pubmed: 34789902
doi: 10.1038/s41586-021-04027-8
pii: 10.1038/s41586-021-04027-8
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.
Langues
eng
Sous-ensembles de citation
IM
Pagination
421-424Commentaires et corrections
Type : CommentIn
Informations de copyright
© 2021. This is a U.S. government work and not under copyright protection in the U.S.; foreign copyright protection may apply.
Références
Mingos, M. & Crabtree, R. Comprehensive Organometallic Chemistry III (Elsevier, 2007).
Zalkin, A. & Raymond, K. N. Structure of di-π-cyclooctatetraeneuranium (uranocene). J. Am. Chem. Soc. 91, 5667–5668 (1969).
doi: 10.1021/ja01048a055
Kealy, T. J. & Pauson, P. L. A new type of organo-iron compound. Nature 168, 1039–1040 (1951).
doi: 10.1038/1681039b0
Hartline, D. R. & Meyer, K. From chemical curiosities and trophy molecules to uranium-based catalysis: developments for uranium catalysis as a new facet in molecular uranium chemistry. JACS Au 1, 698–709 (2021).
doi: 10.1021/jacsau.1c00082
Pagano, J. K. et al. Actinide 2-metallabiphenylenes that satisfy Hückel’s rule. Nature 578, 563–567, (2020).
doi: 10.1038/s41586-020-2004-7
Apostolidis, C., Dutkiewicz, M. S., Kovács, A. & Walter, O. Solid-state structure of tris-cyclopentadienide uranium(III) and plutonium(III). Chem. Eur. J. 24, 2841–2844 (2018).
doi: 10.1002/chem.201704845
Windorff, C. J. et al. Identification of the formal +2 oxidation state of plutonium: synthesis and characterization of {Pu
doi: 10.1021/jacs.7b00706
Formanuik, A. et al. Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy. Nat. Chem. 9, 578–583 (2017).
doi: 10.1038/nchem.2692
Dutkiewicz, M. S., Apostolidis, C., Walter, O. & Arnold, P. L. Reduction chemistry of neptunium cyclopentadienide complexes: from structure to understanding. Chem. Sci. 8, 2553–2561 (2017).
doi: 10.1039/C7SC00034K
Apostolidis, C. et al. A structurally characterized organometallic plutonium(IV) complex. Angew. Chem. Int. Ed. 56, 5066–5070 (2017).
doi: 10.1002/anie.201701858
Dutkiewicz, M. S. et al. Organometallic neptunium(III) complexes. Nat. Chem. 8, 797–802 (2016).
doi: 10.1038/nchem.2520
Liddle, S. T. The renaissance of non-aqueous uranium chemistry. Angew. Chem. Int. Ed. 54, 8604–8641 (2015).
doi: 10.1002/anie.201412168
Goodwin, C. A. P. et al. [Am(C
doi: 10.1002/anie.201905225
Sonnenberger, D. C. & Gaudiello, J. Synthesis and cyclic voltammetric study of bis(pentamethylcyclopentadienyl)neptunium dichloride. J. Less-Common Met. 126, 411–414 (1986).
doi: 10.1016/0022-5088(86)90350-4
Laubereau, P. G. The formation of dicyclopentadienylberkeliumchloride. Inorg. Nucl. Chem. Lett. 6, 611–616 (1970).
doi: 10.1016/0020-1650(70)80057-5
Cary, S. K. et al. A series of dithiocarbamates for americium, curium, and californium. Dalton Trans. 47, 14452–14461 (2018).
doi: 10.1039/C8DT02658K
Polinski, M. J. et al. Unusual structure, bonding and properties in a californium borate. Nat. Chem. 6, 387–392 (2014).
doi: 10.1038/nchem.1896
Sykora, R. E., Assefa, Z., Haire, R. G. & Albrecht-Schmitt, T. E. First structural determination of a trivalent californium compound with oxygen coordination. Inorg. Chem. 45, 475–477 (2006).
doi: 10.1021/ic051667v
Carnall, W. T. A systematic analysis of the spectra of trivalent actinide chlorides in D
doi: 10.1063/1.462278
Carnall, W. T., Fried, S. & Wagner, F. Absorption spectrum of CfCl
doi: 10.1063/1.1679455
Burns, J. H., Peterson, J. R. & Baybarz, R. D. Hexagonal and orthorhombic crystal structures of californium trichloride. J. Inorg. Nucl. Chem. 35, 1171–1177 (1973).
doi: 10.1016/0022-1902(73)80189-7
Laubereau, P. G. & Burns, J. H. Microchemical preparation of tricyclopentadienyl compounds of berkelium, californium, and some lanthanide elements. Inorg. Chem. 9, 1091–1095 (1970).
doi: 10.1021/ic50087a018
Streitwieser, A. & Müller-Westerhoff, U. Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals. J. Am. Chem. Soc. 90, 7364–7364 (1968).
doi: 10.1021/ja01028a044
Minasian, S. G. et al. New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory. Chem. Sci. 5, 351–359 (2014).
doi: 10.1039/C3SC52030G
Evans, W. J. Tutorial on the role of cyclopentadienyl ligands in the discovery of molecular complexes of the rare-earth and actinide metals in new oxidation states. Organometallics 35, 3088–3100 (2016).
doi: 10.1021/acs.organomet.6b00466
Hayton, T. W. Recent developments in actinide-ligand multiple bonding. Chem. Commun. 49, 2956–2973 (2013).
doi: 10.1039/c3cc39053e
Jones, M. B. & Gaunt, A. J. Recent developments in synthesis and structural chemistry of nonaqueous actinide complexes. Chem. Rev. 113, 1137–1198 (2013).
doi: 10.1021/cr300198m
Baumgärtner, F., Fischer, E. O., Kanellakopulos, B. & Laubereau, P. Tri(cyclopentadienyl)americium(III). Angew. Chem. Int. Ed. 5, 134–135 (1966).
doi: 10.1002/anie.196601342
Laubereau, P. G. & Burns, J. H. Tricyclopentadienyl-curium. Inorg. Nucl. Chem. Lett. 6, 59–63 (1970).
doi: 10.1016/0020-1650(70)80285-9
Kirker, I. & Kaltsoyannis, N. Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp
doi: 10.1039/C0DT01018A
Strittmatter, R. J. & Bursten, B. E. Bonding in tris(η
doi: 10.1021/ja00002a024
Kozimor, S. A. et al. Trends in covalency for d- and f-element metallocene dichlorides identified using chlorine K-edge X-ray absorption spectroscopy and time-dependent density functional theory. J. Am. Chem. Soc. 131, 12125–12136 (2009).
doi: 10.1021/ja9015759
Arney, D. S. J. & Burns, C. J. Synthesis and properties of high-valent organouranium complexes containing terminal organoimido and oxo functional groups. A new class of organo-f-element complexes. J. Am. Chem. Soc. 117, 9448–9460 (1995).
doi: 10.1021/ja00142a011
Apostolidis, C. et al. [An(H
doi: 10.1002/anie.201001077
Polinski, M. J. et al. Chirality and polarity in the f‐block borates M
doi: 10.1002/chem.201403820
Cary, S. K. et al. Emergence of californium as the second transitional element in the actinide series. Nat. Commun. 6, 6827 (2015).
doi: 10.1038/ncomms7827
Galley, S. S. et al. Synthesis and characterization of tris-chelate complexes for understanding f-orbital bonding in later actinides. J. Am. Chem. Soc. 141, 2356–2366 (2019).
doi: 10.1021/jacs.8b10251
Shannon, R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. A 32, 751–767 (1976).
doi: 10.1107/S0567739476001551
Schumann, H., Glanz, M., Hemling, H. & Ekkehard Hahn, F. Metallorganische Verbindungen der Lanthanoide. 93 [1]. Tetramethylcyclopentadienyl-Komplexe ausgewählter 4f-Elemente. Z. Anorg. Allg. Chem. 621, 341–345 (1995).
doi: 10.1002/zaac.19956210302
Jenkins, T. F. et al. Tetramethylcyclopentadienyl ligands allow isolation of Ln(II) ions across the lanthanide series in [K(2.2.2-cryptand)][(C
doi: 10.1021/acs.organomet.8b00557