Seminal theoretical studies in f element chemistry by Bursten, et al. focused on tris(cyclopentadienyl) metal complexes. In recent years, these early studies have proven to be prophetic. The recent isolation of the (Cp'3U)1-, (Cp"3U)1-, and (Cp"3Th)1- anions [Cp' = C5H4SiMe3 ; Cp" = C5H3(SiMe3)2] has demonstrated that +2 is a viable formal oxidation state for uranium and thorium in molecular species. The physical properties of these complexes are consistent with the early theoretical studies and DFT studies that suggest that in these complexes U2+ is a 5f36d1 ion and Th2+ is 6d2. The latter configuration is the first of its kind in the periodic table and that expected for fourth row transition metal ions such as Rf2+ and Db3+. Recent studies of the reactivity of these complexes to probe the nature of the new electron configurations will be described as well as efforts to synthesize new classes of tris(cyclopentadienyl) complexes.

Recent advances in the chemistry of tris(cyclopentadienyl) rare-earth and actinide metal complexes

253rd National Meeting (2017)

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