Octakis(tert-butoxo)dicerium(IV) [Ce2(OtBu)8]: Synthesis, Characterization, Decomposition, and Reactivity

An advanced synthesis for the homometallic derivative [Ce2(OtBu)8] (1) starting from [Ce­(OtBu)2{N­(SiMe3)2}2] was developed. Structural characterization of a cerium­(IV) complex and its decomposition products confirmed the coexistence of both ether elimination and Ce–O bond cleavage processes, which lead to the formation of [Ce3O­(OtBu)10] and [Ce3(OtBu)11] (2) derivatives, respectively. Variable-temperature NMR spectroscopy under strict exclusion of moisture enabled insight into the decomposition processes in noncoordinating solvents and at elevated temperature. In addition, structural analysis of the heterovalent 2 and of two new complexes of the general formula [Ce2(OtBu)8(L)] [L = HOtBu (3), OCPh2 (4)] is described.