Despite the dearth of organometallic chemistry throughout the periodic table, organoplutonium chemistry remains rather under-developed due to the radioactivity of this element. For example, although the first organometallic plutonium compound, Pu(C5H5)3, was first synthesized over 50 years ago, yet the structural characterization was reported just this year. To date only four organoplutonium complexes have been characterized by single crystal X-ray diffraction, all of which have been reported in the last two years. We report here the reactivity of reduced solutions of Pu(C5H4SiMe3)3/KC8 with C8H8 leading the crystallographic characterization of the reduced plutonocene [K(2.2.2-cryptand)][Pu(C8H8)2], and the tetrakis cyclopentadienyl ligand redistribution product, [K(2.2.2-cryptand)][Pu(C5H4SiMe3)4]. The reaction products are similar to those obtained when [K(2.2.2-cryptand)][Ln(C5H4SiMe3)3] are reacted with C8H8, and contrast the corresponding chemistry with [An(C5H3RSiMe)3]− (An = Th, U; R = H, SiMe3) where only tetravalent cyclooctatetraenide products are isolated. Finally, [Pu(C8H8)2]− was oxidized to Pu(C8H8)2 and crystallographically characterized for the first time, despite being synthesized in 1970.

Probing plutonium redox behavior with cyclooctatetraene

2019 Spring National Meeting

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