Although organometallic chemistry has been heavily studied 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, no full structural characterizations have been reported in the literature on any organoplutonium complexes. We now report the synthesis and crystallographic-characterization of the Pu(III) complex Pu[C5H3(SiMe3)2]3. This complex was prepared for evaluation as a possible precursor to a Pu(II) product. Reduction of the silylcyclopentadienyl complexes M(C5H4SiMe3)3 and M[C5H3(SiMe3)2]3 have recently provided the first examples of M(II) complexes for yttrium and all the lanthanides as well as uranium and thorium. Reduction of Pu[C5H3(SiMe3)2]3 with potassium graphite in the presence of 2.2.2-cryptand proceeds similarly and gives crystals of the first example of Pu2+ as [K(2.2.2-cryptand)]{Pu[C5H3(SiMe3)2]3} which has been characterized by X-ray crystallography, UV-VIS-NIR and 1H NMR spectroscopies.

Synthesis and x-ray crystallographic characterization of low valent organoplutonium complexes: Identification of plutonium in the +2 oxidation state

253rd National Meeting (2017)

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