Facile and Reversible Formation of Iron(III)–Oxo–Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III)

Ceric ammonium nitrate (CAN) or Ce^IV(NH₄)₂(NO₃)₆ is often used in artificial water oxidation and generally considered to be an outer-sphere oxidant. Herein we report the spectroscopic and crystallographic characterization of [(N4Py)Fe^III-O-Ce^IV(OH₂)(NO₃)₄]⁺ (3), a complex obtained from the reaction of [(N4Py)Fe^II(NCMe)]²⁺ with 2 equiv CAN or [(N4Py)Fe^IV=O]²⁺ (2) with Ce^III(NO₃)₃ in MeCN. Surprisingly, the formation of 3 is reversible, the position of the equilibrium being dependent on the MeCN/water ratio of the solvent. These results suggest that the Fe^IV and Ce^IV centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S=1 Fe^IV in 2 to S=5/2 in 3, which is found to be facile despite the formal spin-forbidden nature of this process. This observation suggests that Fe^IV=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier.