Isolation of a californium(II) crown–ether complex

Poe, Todd N.; Ramanantoanina, Harry; Sperling, Joseph M.; Wineinger, Hannah B.; Rotermund, Brian M.; Brannon, Jacob; Bai, Zhuanling; Scheibe, Benjamin; Beck, Nicholas; Long, Brian N.; Justiniano, Samantha; Albrecht-Schönzart, Thomas E.; Celis-Barros, Cristian

doi:10.1038/s41557-023-01170-9

Isolation of a californium(II) crown–ether complex

Journal Article · Mon Mar 27 04:00:00 EDT 2023 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-023-01170-9· OSTI ID:2371570

^[1]; Ramanantoanina, Harry ^[2]; ^[3]; Wineinger, Hannah B. ^[3]; ^[4]; ^[4]; ^[4]; Scheibe, Benjamin ^[3]; Beck, Nicholas ^[4]; Long, Brian N. ^[4]; Justiniano, Samantha ^[4]; ^[3]; ^[3]

Florida State University, Tallahassee, FL (United States); Colorado School of Mines
Karlsruhe Institute of Technology (Germany)
Colorado School of Mines, Golden, CO (United States)
Florida State University, Tallahassee, FL (United States)

The actinides, from californium to nobelium (Z = 98–102), are known to have an accessible +2 oxidation state. Understanding the origin of this chemical behaviour requires characterizing Cf^II materials, but investigations are hampered by the fact that they have remained dificult to isolate. This partly arises from the intrinsic challenges of manipulating this unstable element, as well as a lack of suitable reductants that do not reduce Cf^III to Cf°. Here we show that a Cf^II crown–ether complex, Cf(18-crown-6)I₂, can be prepared using an Al/Hg amalgam as a reductant. Spectroscopic evidence shows that Cf^III can be quantitatively reduced to Cf^II, and rapid radiolytic re-oxidation in solution yields co-crystallized mixtures of Cf^II and Cf^III complexes without the Al/Hg amalgam. Furthermore, quantum-chemical calculations show that the Cf– ligand interactions are highly ionic and that 5f/6d mixing is absent, resulting in weak 5f→5f transitions and an absorption spectrum dominated by 5f→6d transitions.

View Accepted Manuscript (DOE)

Research Organization:: Colorado School of Mines, Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0010677; SC0010677

OSTI ID:: 2371570

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 5 Vol. 15; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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