Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {PuII[C5H3(SiMe3)2]3}<sup/>

Cory J Windorff; Guo P Chen; Justin N Cross; William J Evans; Filipp Furche; Andrew J Gaunt; Michael T Janicke; Stosh A Kozimor; Brian L Scott

doi:10.1021/jacs.7b00706

Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {Pu^II[C₅H₃(SiMe₃)₂]₃}<sup/>

J Am Chem Soc. 2017 Mar 22;139(11):3970-3973. doi: 10.1021/jacs.7b00706. Epub 2017 Mar 13.

Authors

Cory J Windorff¹, Guo P Chen¹, Justin N Cross, William J Evans¹, Filipp Furche¹, Andrew J Gaunt, Michael T Janicke, Stosh A Kozimor, Brian L Scott

Affiliation

¹ Department of Chemistry, University of California , Irvine, California 92697-2025, United States.

PMID: 28235179
DOI: 10.1021/jacs.7b00706

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 Pu²⁺ in [K(2.2.2-cryptand)][Pu^IICp″₃], Cp″ = C₅H₃(SiMe₃)₂. The synthetic precursor Pu^IIICp″₃ is also reported, comprising the first structural characterization of a Pu-C bond. Absorption spectroscopy and DFT calculations indicate that the Pu²⁺ ion has predominantly a 5f⁶ electron configuration with some 6d mixing.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.