A Ce4+ Aluminum Hydride Complex.

Complexes of reducing hydride ligands by high-oxidation state cerium are unknown due to the fundamental mismatch in their redox chemistry. Herein we report the synthesis, characterization, and reactivity of the first example of a Ce4+ aluminum hydride complex. Synthetic strategies adapted from the preparation of Ce4+ alkyl complexes facilitated the isolation of [Ce4+(κ2-H3AlC(TMS)3)(NP(tBu)3)3] (CeHAl). The bonding and structure of this complex is characterized by single-crystal XRD, NMR, and UV-vis-NIR spectroscopy, and DFT computations. The fundamental reactivity profile is evaluated by cyclic voltammetry and small-molecule reactions.