Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of PuII[C5H3(SiMe3)2]3−

2017/02/24 by Cory J. Windorff, Guo P. Chen, Justin N. Cross +6 · 1 citation
Chemistry · Environmental Science · Materials Science · #Radioactive element chemistry and processing #Chemical Synthesis and Characterization #Lanthanide and Transition Metal Complexes

paper · doi:10.1021/jacs.7b00706

openalex publication_date 2017/02/24 · openalex created_date 2017/03/03 · openalex updated_date 2026/08/01

Abstract

Over 70 years of chemical investigations have shown that plutonium exhibits some of the most complicated chemistry in the periodic table. Six Pu oxidation states have been unambiguously confirmed (0 and +3 to +7), and four different oxidation states can exist simultaneously in solution. We report a new formal oxidation state for plutonium, namely Pu 2+ in [K(2.2.2-cryptand)][Pu II Cp″ 3 ], Cp″ = C 5 H 3 (SiMe 3 ) 2 . The synthetic precursor Pu III Cp″ 3 is also reported, comprising the first structural characterization of a Pu–C bond. Absorption spectroscopy and DFT calculations indicate that the Pu 2+ ion has predominantly a 5f 6 electron configuration with some 6d mixing.

Citations

• Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States
• Reduction chemistry of neptunium cyclopentadienide complexes: from structure to understanding

Cited by

• Plutonium compounds [wikipedia]