Electrochemistry of Kinetically Inert Cerium Aryloxide Complexes Supported by Interligand Hydrogen Bonds

"We present some of our recent efforts in the development of predictive, directed oxidation chemistry of cerium(III) complexes under non-aqueous conditions. The electrochemistry of cerium(III)- alkali metal heterobimetallic aryloxide complexes is reported and compared with cerium aryloxide complexes that are kinetically stabilized by hydrogen bonding cations that span between the complexed aryloxide ligands. Comparative electrochemical measurements reveal differences between the heterobimetallic complexes and the hydrogen-bonded complexes.INTRODUCTIONThe rare earth elements comprise the lanthanides, La–Lu, and the element yttrium (Aspinall, 2001). Rare earth ores such as monazite, LnPO4, and bastnäsite, LnFCO3, typically bear mixtures of light rare earths: La–Sm while monazite, LnPO4, contains mixtures of heavy rare earths (Eu–Lu) (Cotton, 2006). Pure rare earth elements typically are isolated using a liquid-liquid separations process.(Bautista, 1995) The hydrometallurgy of these elements is a difficult problem because the separation factors between neighboring rare earths, which are predicated on the small differences in the sizes of the trivalent ions, are quite small (Cox, 1992). The element cerium, with its 4f1 electronic configuration in the trivalent state, is unique among the rare earth elements due to a relatively accessible 4f0 electronic configuration. The accessibility of the 4f0 configuration underlies the chemistry of cerium(IV), the only rare earth ion with molecular chemistry in the tetravalent oxidation state (Cotton, 2006). Cerium is trivially separated from mixtures of light rare earths by making use of its unique oxidation chemistry. In an effort to extend separations chemistry by oxidation reactions to other rare earth elements such as terbium and praseodymium, the solution electrochemistry of well-defined cerium complexes is of interest."