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

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

doi:10.1002/anie.201704322

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

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

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	9091-9095
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	31
DOIs	https://doi.org/10.1002/anie.201704322
State	Published - Jul 24 2017

Bibliographical note

Funding Information:
This work was supported by a grant from the U.S. National Institutes of Health (GM-38767 to L.Q.). XAS data were collected at the Stanford Synchrotron Radiation Lightsource, which is supported by the U.S. DOE under Contract No. DE-AC02-76SF00515. Use of Beamline 7-3 is supported by the DOE Office of Biological and Environmental Research and the National Institutes of Health, National Institute of General Medical Sciences (including P41GM103393). J.E.M.N.K. thanks the Alexander von Humboldt Foundation for a Feodor Lynen Research Fellowship. We thank Dr. Victor J. Young, Jr. of the University of Minnesota Crystallographic Facility for his valuable advice in the crystallographic analysis.

Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

cerium
electron transfer
iron
spin crossover
water oxidation

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https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5598155

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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 = "Ceric ammonium nitrate (CAN) or CeIV(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)FeIII-O-CeIV(OH2)(NO3)4]+ (3), a complex obtained from the reaction of [(N4Py)FeII(NCMe)]2+ with 2 equiv CAN or [(N4Py)FeIV=O]2+ (2) with CeIII(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 FeIV and CeIV centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S=1 FeIV 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 FeIV=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier.",

keywords = "cerium, electron transfer, iron, spin crossover, water oxidation",

author = "Apparao Draksharapu and Waqas Rasheed and Klein, {Johannes E.M.N.} and Lawrence Que",

note = "Funding Information: This work was supported by a grant from the U.S. National Institutes of Health (GM-38767 to L.Q.). XAS data were collected at the Stanford Synchrotron Radiation Lightsource, which is supported by the U.S. DOE under Contract No. DE-AC02-76SF00515. Use of Beamline 7-3 is supported by the DOE Office of Biological and Environmental Research and the National Institutes of Health, National Institute of General Medical Sciences (including P41GM103393). J.E.M.N.K. thanks the Alexander von Humboldt Foundation for a Feodor Lynen Research Fellowship. We thank Dr. Victor J. Young, Jr. of the University of Minnesota Crystallographic Facility for his valuable advice in the crystallographic analysis. Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2017",

month = jul,

day = "24",

doi = "10.1002/anie.201704322",

language = "English (US)",

volume = "56",

pages = "9091--9095",

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T1 - Facile and Reversible Formation of Iron(III)–Oxo–Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III)

AU - Draksharapu, Apparao

AU - Rasheed, Waqas

AU - Klein, Johannes E.M.N.

AU - Que, Lawrence

N1 - Funding Information: This work was supported by a grant from the U.S. National Institutes of Health (GM-38767 to L.Q.). XAS data were collected at the Stanford Synchrotron Radiation Lightsource, which is supported by the U.S. DOE under Contract No. DE-AC02-76SF00515. Use of Beamline 7-3 is supported by the DOE Office of Biological and Environmental Research and the National Institutes of Health, National Institute of General Medical Sciences (including P41GM103393). J.E.M.N.K. thanks the Alexander von Humboldt Foundation for a Feodor Lynen Research Fellowship. We thank Dr. Victor J. Young, Jr. of the University of Minnesota Crystallographic Facility for his valuable advice in the crystallographic analysis. Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/7/24

Y1 - 2017/7/24

N2 - Ceric ammonium nitrate (CAN) or CeIV(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)FeIII-O-CeIV(OH2)(NO3)4]+ (3), a complex obtained from the reaction of [(N4Py)FeII(NCMe)]2+ with 2 equiv CAN or [(N4Py)FeIV=O]2+ (2) with CeIII(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 FeIV and CeIV centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S=1 FeIV 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 FeIV=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier.

AB - Ceric ammonium nitrate (CAN) or CeIV(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)FeIII-O-CeIV(OH2)(NO3)4]+ (3), a complex obtained from the reaction of [(N4Py)FeII(NCMe)]2+ with 2 equiv CAN or [(N4Py)FeIV=O]2+ (2) with CeIII(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 FeIV and CeIV centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S=1 FeIV 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 FeIV=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier.

KW - cerium

KW - electron transfer

KW - iron

KW - spin crossover

KW - water oxidation

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U2 - 10.1002/anie.201704322

DO - 10.1002/anie.201704322

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VL - 56

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EP - 9095

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 31

ER -

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

Abstract

Bibliographical note

Keywords

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