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

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 in [K(2.2.2-cryptand)][PuCp″], Cp″ = CH(SiMe). The synthetic precursor PuCp″ is also reported, comprising the first structural characterization of a Pu-C bond. Absorption spectroscopy and DFT calculations indicate that the Pu ion has predominantly a 5f electron configuration with some 6d mixing.

Solid‐State Structure of Tris‐Cyclopentadienide Uranium(III) and Plutonium(III)

“…This is also the case for the recently studied complex Pu(CpTMS 2 ) 3 5. This behaviour supports the high coordinative flexibility of both the Cp rings and the actinide ions.…”

A Structurally Characterized Organometallic Plutonium(IV) Complex

“…The synthetic protocol (that is,o xidation of the anionic Pu III sandwich complex Li[Pu(1,4-COT'') 2 ]( 3)w ith anhydrous CoCl 2 )w as inspired by our previously discovered method to convert the anionic lanthanide(III) sandwich complexes [Ln(COT'') 2 ] À into the linear neutral triple-decker sandwich species Ln 2 (COT'') 3 .Blood-red crystals of 4 were obtained in 84 %yield after extraction with n-pentane.Compound 4 is the first organometallic Pu IV complex structurally characterized by X-ray diffraction. [67] Thecrystal structure determination of 4 revealed as andwich structure with one 1,3-substituted COT'' ring while the other ring retains the original 1,4substitution pattern. Thee lectronic structure of 4 has been elucidated by computational methods,r evealing ap lausible cause for this unexpected silyl group migration.…”

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

“…[7] The AnO 2 + oxidation states assigned here are showni nT able 4a long with the known (and proposed)actinideoxidationstates. [25][26][27][28][29][30][31] Naturalpopulation analysis (NPA)…”