Stabilization of Pu(IV) in PuBr(OPCy) and Comparisons with Structurally Similar ThX(OPR) (R = Cy, Ph) Molecules.

The pursuit of a trivalent plutonium halide phosphine oxide compound, e.g., "PuBr(OPR)," instead led to the isolation of the tetravalent -PuBr(OPCy), , compound by spontaneous oxidation of Pu.

Expanding Transuranium Organoactinide Chemistry: Synthesis and Characterization of (Cp'M)(μ-4,4'-bpy) (M = Ce, Np, Pu).

Dinuclear, organometallic, transuranium compounds, (Cp'M)(μ-4,4'-bpy) (Cp' = trimethylsilylcyclopentadienide, 4,4'-bpy = 4,4'-bipyridine, M = Ce, Np, Pu), reported herein provide a rare opportunity to probe the nature of actinide-carbon bonding. Significant splitting of the f-f transitions results from the unusual coordination environment in these complexes and leads to electronic properties that are currently restricted to organoactinide systems. Structural and spectroscopic characterization in the solid state and in solution for (Cp'M)(μ-4,4'-bpy) (M = Np, Pu) are reported, and their structural metrics are compared to a cerium analogue.

Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution.

Despite the significant impact of radiation-induced redox reactions on the accessibility and lifetimes of actinide oxidation states, fundamental knowledge of aqueous actinide metal ion radiation chemistry is limited, especially for the late actinides. A quantitative understanding of these intrinsic radiation-induced processes is essential for investigating the fundamental properties of these actinides. We present here a picosecond electron pulse reaction kinetics study into the radiation-induced redox chemistry of trivalent berkelium (Bk(III)) and californium (Cf(III)) ions in acidic aqueous solutions at ambient temperature.

A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes.

An approach to obtaining substantial amounts of data from a hazardous starting material that can only be obtained and handled in small quantities is demonstrated by the investigation of a single small-scale reaction of cyclooctatetraene, CH, with a solution obtained from the reduction of Cp'Pu (Cp' = CHSiMe) with potassium graphite. This one reaction coupled with oxidation of a product has provided single-crystal X-ray structural data on three organoplutonium compounds as well as information on redox chemistry thereby demonstrating an efficient route to new reactivity and structural information on this highly radioactive element. The crystal structures were obtained from the reduction of CH by a putative Pu(II) complex, (Cp'Pu), generated in situ, to form the Pu(III) cyclooctatetraenide complex, [K(crypt)][(CH)Pu], , and the tetra(cyclopentadienyl) Pu(III) complex, [K(crypt)][Cp'Pu], .