Facile Oxidation of Ce(III) to Ce(IV) Using Cu(I) Salts.

The synthesis, luminescence, and electrochemical properties of the Ce(III) compound, [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(THF)], 1 , were investigated. Based on the electrochemical data, treatment of 1 with CuX (X = Cl, Br, I) results in the formation of the corresponding Ce(IV) complexes, [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(X)]. Each complex has been characterized using NMR, IR, and UV-vis spectroscopy as well as structurally determined using X-ray crystallography. Additionally, the treatment of [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(Br)] with AgF results in the formation of the putative [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(F)]. The electronic structure of these Ce(IV)-X complexes was investigated by bond analyses and the Ce(IV)-F moiety using quantum chemistry NMR calculations.