Despite the widespread applications of cerium(III) and cerium(IV) in oxidation, catalytic, and materials chemistry there are few rational routes to prepare functionalized cerium(IV) complexes. Here, we explore the structural and redox effects of hydrogen bonding interactions in the secondary coordination sphere with the goal of promoting the oxidation of cerium(III) ions. In studying complexes of cerium with 2-naphtholate, we have observed that the installation of hydrogen bonding moieties in the secondary coordination sphere drastically affect the structure, stability, and redox properties when compared to the alkali metal analogs of this system. By introducing a hydrogen bond donor, we have the ability to tune two parameters in determining the structure and reactivity of the cerium complexes: the steric and electronic environment of the ligand, and the steric contribution from the hydrogen bond donors.

Stabilizing lanthanide-aryloxide complexes with noncovalent interactions

244th National Meeting (2012)

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