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

Cory J. Windorff^†‡, Guo P. Chen^†, Justin N. Cross‡, William J. Evans^*^†

, Filipp Furche^*^†

, Andrew J. Gaunt^*‡

, Michael T. Janicke‡, Stosh A. Kozimor^*‡, and Brian L. Scott§

^† Department of Chemistry, University of California, Irvine, California 92697-2025, United States

^‡Chemistry Division and ^§Materials Physics and Applications Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States

J. Am. Chem. Soc., 2017, 139 (11), pp 3970–3973

DOI: 10.1021/jacs.7b00706

Publication Date (Web): February 24, 2017

Copyright © 2017 American Chemical Society

*gaunt@lanl.gov, *stosh@lanl.gov, *filipp.furche@uci.edu, *wevans@uci.edu

Cite this:J. Am. Chem. Soc. 139, 11, 3970-3973

Abstract

Abstract Image

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.

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.7b00706.

Complete experimental details; NMR, UV/vis/NIR, and IR spectra; reactivity studies; computational details; and crystallographic data (PDF)
Crystallographic data for 1 (CIF)
Crystallographic data for 2 (CIF)
Cartesian coordinates of the DFT equilibrium structures in xyz format (TXT)

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