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

Draksharapu, Apparao; Rasheed, Waqas; Klein, Johannes E. M. N.; Que, Jr., Lawrence

doi:10.1002/ange.201704322

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

Journal Article · 26 June 2017 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201704322 · OSTI ID:1374914

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Department of Chemistry and Center for Metals in Biocatalysis University of Minnesota Minneapolis MN 55455 USA

Abstract Ceric ammonium nitrate (CAN) or Ce ^IV (NH ₄ ) ₂ (NO ₃ ) 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 (OH ₂ )(NO ₃ ) 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 (NO ₃ ) 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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1374914

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 31 Vol. 129; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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