Recently, a series of trivalent and tetravalent cerium and terbium complexes supported by the bulky, weak-field imidophosphorane ligand, [NP(1,2-bis-tBu-diamidoethane)(NEt2))4]1-, have been isolated. Prior to our studies (and a contemporaneous example of tetravalent terbium in [Tb(OSi(OtBu)3)3(k2-OSi(OtBu)3]), no complexes of tetravalent lanthanides, other than cerium, had been isolated and fully characterized, despite significant efforts. The crystal structures of the four-coordinate, highly symmetric (S4), tetravalent complexes, [Ln(NP(1,2-bis-tBu-diamidoethane)(NEt2))4] ( Ln = Ce or Tb), are isotypic which enables, for the first-time, a thorough comparison of the physical and chemical properties in solution and solid-state of two tetravalent lanthanide ions. In this presentation, we will discuss recent structural, electrochemical, magnetic, EPR, theoretical, and L3-edge XANES studies of these complexes to investigate their electronic structure. Opportunities for expanding the known tetravalent lanthanides will be discussed in the context of these results.

Synthesis and spectroscopy of tetravalent lanthanide (Ce and Tb) complexes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.