Cerium Tetrakis(tropolonate) and Cerium Tetrakis(acetylacetonate) Are Not Diamagnetic but Temperature-Independent Paramagnets

A new synthesis of cerium tetrakis(tropolonate), Ce(trop)₄, where trop is deprotonated 2-hydroxy-2,4,6-cycloheptatrienone) or Ce(O₂C₇H₅)₄, is developed that results in dark-purple crystals whose X-ray crystal structure shows that the geometry of the eight-coordinate compound closely resembles a D_2d dodecahedron, based on shape parameters. The magnetic susceptibility as a function of the temperature (4-300 K) shows that it is a temperature-independent paramagnet, χ = 1.2(3) × 10^-4 emu/mol, and the L_III-edge X-ray absorption near-edge structure spectrum shows that the molecule is multiconfigurational, comprised of a f¹:f⁰ configuration mixture in a 50:50 ratio. Ce(acac)₄ and Ce(tmtaa)₂ (where acac is acetylacetonate and tmtaaH₂ is tetramethyldibenzotetraaza[14]annulene) have similar physical properties, as does the solid-state compound CeO₂. The concept is advanced that trop^-, acac^-, tmtaa^2-, cot^2-, and O^2- are redox-active ligands that function as electron donors, rendering the classification of these compounds according to their oxidation numbers misleading because their magnetic susceptibilities, χ, are positive and their effective magnetic moments, μ_eff, lie in the range of 0.1-0.7 μ_B at 300 K.