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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Department of Chemistry and Center for Metals in Biocatalysis University of Minnesota Minneapolis MN 55455 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1374914
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Name: Angewandte Chemie Journal Volume: 129 Journal Issue: 31; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Draksharapu, Apparao, Rasheed, Waqas, Klein, Johannes E. M. N., and Que, Jr., Lawrence. Facile and Reversible Formation of Iron(III)–Oxo–Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III). Germany: N. p., 2017. Web. doi:10.1002/ange.201704322.
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Draksharapu, Apparao, Rasheed, Waqas, Klein, Johannes E. M. N., & Que, Jr., Lawrence. Facile and Reversible Formation of Iron(III)–Oxo–Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III). Germany. https://doi.org/10.1002/ange.201704322
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Draksharapu, Apparao, Rasheed, Waqas, Klein, Johannes E. M. N., and Que, Jr., Lawrence. Tue . "Facile and Reversible Formation of Iron(III)–Oxo–Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III)". Germany. https://doi.org/10.1002/ange.201704322.
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@article{osti_1374914,
title = {Facile and Reversible Formation of Iron(III)–Oxo–Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III)},
author = {Draksharapu, Apparao and Rasheed, Waqas and Klein, Johannes E. M. N. and Que, Jr., Lawrence},
abstractNote = {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.},
doi = {10.1002/ange.201704322},
journal = {Angewandte Chemie},
number = 31,
volume = 129,
place = {Germany},
year = {Tue Jun 27 00:00:00 EDT 2017},
month = {Tue Jun 27 00:00:00 EDT 2017}
}
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https://doi.org/10.1002/ange.201704322
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