The first crystallographically-characterized Th(III) complex Cp"3Th [Cp" = C5H3(SiMe3)2] was reported in 1986 by Lappert. Since then, the Th(III) ion has been crystallographically characterized in eleven unique ligand environments. With such few examples, the reactivity patterns of Th(III) have not been as explored as well as related U(III) compounds. In the case of Th(II), there is only a single example in the literature, namely [Cp"3Th]1-, which was formed by chemical reduction of Cp"3Th. In pursuit of new Th(III) complexes, a new synthesis of Th(II) was discovered. Addition of KH to Cp"3Th formed [Cp"3Th]1- and Cp"3ThH, not the expected [Cp"3ThH]1- product. This talk will discuss how the addition of MX (M = alkali metal, X = anion) to (C5R5)3Th complexes in the presence of an alkali metal chelate leads to disproportionation into [M(chelate)][Cp"3Th] and Cp"3ThX. Potential reaction pathways based on electrochemical data and the outlook for this type of reaction will be discussed.

Disproportionation of Th(III) complexes to form Th(II) and Th(IV) complexes

ACS Spring 2022

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