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

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, C₈H₈, with a solution obtained from the reduction of Cp'₃Pu (Cp' = C₅H₄SiMe₃) 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 C₈H₈ by a putative Pu(II) complex, (Cp'₃Pu^II)^1-, generated in situ, to form the Pu(III) cyclooctatetraenide complex, [K(crypt)][(C₈H₈)₂Pu^III], 1-Pu, and the tetra(cyclopentadienyl) Pu(III) complex, [K(crypt)][Cp'₄Pu^III], 2-Pu. Oxidation of the sample of 1-Pu with Ag(I) afforded a third organoplutonium complex that has been structurally characterized for the first time, (C₈H₈)₂Pu^IV, 3-Pu. Complexes 1-Pu and 3-Pu contain Pu sandwiched between parallel (C₈H₈)^2- rings. The (Cp'₄Pu^III)^- anion in 2-Pu features three η⁵-Cp' rings and one η¹-Cp' ring, which is a rare example of a formal Pu-C η¹-bond. In addition, this study addresses the challenge of small-scale synthesis imparted by radiological and material availability of transuranium isotopes, in particular that of pure metal samples. A route to an anhydrous Pu(III) starting material from the more readily available Pu^IVO₂ was developed to facilitate reproducible syntheses and allow complete spectroscopic analysis of 1-Pu and 2-Pu. Pu^IVO₂ was converted to Pu^IIIBr₃(DME)₂ (DME = CH₃OCH₂CH₂OCH₃) and subsequently Pu^IIIBr₃(THF), which was used to independently synthesize 1-Pu, 2-Pu, and 3-Pu.