Octakis(<i>tert</i>-butoxo)dicerium(IV) [Ce<sub>2</sub>(O<sup><i>t</i></sup>Bu)<sub>8</sub>]: Synthesis,
Characterization, Decomposition, and Reactivity
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Abstract
An advanced synthesis for the homometallic
derivative [Ce<sub>2</sub>(O<sup><i>t</i></sup>Bu)<sub>8</sub>] (<b>1</b>) starting from [Ce(O<sup><i>t</i></sup>Bu)<sub>2</sub>{N(SiMe<sub>3</sub>)<sub>2</sub>}<sub>2</sub>] 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 [Ce<sub>3</sub>O(O<sup><i>t</i></sup>Bu)<sub>10</sub>] and [Ce<sub>3</sub>(O<sup><i>t</i></sup>Bu)<sub>11</sub>] (<b>2</b>) 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 <b>2</b> and of two new complexes of the general formula [Ce<sub>2</sub>(O<sup><i>t</i></sup>Bu)<sub>8</sub>(L)] [L = HO<sup><i>t</i></sup>Bu (<b>3</b>), OCPh<sub>2</sub> (<b>4</b>)] is described
