Acid-Triggered O−O Bond Heterolysis of a Nonheme FeIII(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds

Joan Serrano-Plana; Ferran Acuña-Parés; Valeria Dantignana; Williamson N. Oloo; Esther Castillo; Apparao Draksharapu; Christopher J. Whiteoak; Vlad Martin-Diaconescu; Manuel G. Basallote; Josep M. Luis; Lawrence Que; Miquel Costas; Anna Company

doi:10.1002/chem.201704851

Acid-Triggered O−O Bond Heterolysis of a Nonheme Fe^III(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds

Joan Serrano-Plana, Ferran Acuña-Parés, Valeria Dantignana, Williamson N. Oloo, Esther Castillo, Apparao Draksharapu, Christopher J. Whiteoak, Vlad Martin-Diaconescu, Manuel G. Basallote, Josep M. Luis, Lawrence Que, Miquel Costas, Anna Company

Chemistry (Twin Cities)

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

39 Scopus citations

Abstract

A novel hydroperoxoiron(III) species [Fe^III(OOH)(MeCN)(PyNMe₃)]²⁺ (3) has been generated by reaction of its ferrous precursor [Fe^II(CF₃SO₃)₂(PyNMe₃)] (1) with hydrogen peroxide at low temperatures. This species has been characterized by several spectroscopic techniques and cryospray mass spectrometry. Similar to most of the previously described low-spin hydroperoxoiron(III) compounds, 3 behaves as a sluggish oxidant and it is not kinetically competent for breaking weak C−H bonds. However, triflic acid addition to 3 causes its transformation into a much more reactive compound towards organic substrates that is capable of oxidizing unactivated C−H bonds with high stereospecificity. Stopped-flow kinetic analyses and theoretical studies provide a rationale for the observed chemistry, a triflic-acid-assisted heterolytic cleavage of the O−O bond to form a putative strongly oxidizing oxoiron(V) species. This mechanism is reminiscent to that observed in heme systems, where protonation of the hydroperoxo intermediate leads to the formation of the high-valent [(Porph^.)Fe^IV(O)] (Compound I).

Original language	English (US)
Pages (from-to)	5331-5340
Number of pages	10
Journal	Chemistry - A European Journal
Volume	24
Issue number	20
DOIs	https://doi.org/10.1002/chem.201704851
State	Published - Apr 6 2018

Bibliographical note

Funding Information:
Financial support for this work was provided by the European Commission (2011-CIG-303522 to A.C., 675020-MSCA-ITN-2015-ETN to M.C.), the Spanish Ministry of Science (CTQ2015-70795-P to M.C., CTQ2016-77989-P to A.C., CTQ2014-52525-P to J.M.L., CTQ2015-65707-C2-2-P to M.G.B., and CSD2010-00065 to M.C and M.G.B.) and Generalitat de Catalunya (ICREA Academia Award to M.C. and 2014 SGR 862). The Spanish Ministry of Science is also acknowledged for a Ramón y Cajal contract to A.C. (RYC-2011–08683). The work conducted at the University of Minnesota has been supported by the US National Science Foundation (grant CHE1665391 to L.Q.). XAS data was collected at the SOLEIL synchrotron SAMBA beamline (proposal 20150413). We would like to thank the beamline staff for their help with experiment preparation in particular Dr. Andrea Zitolo.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

C−H bond activation
density functional calculations
hydroperoxoiron(III)
oxidation
stereospecific

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Serrano-Plana, J., Acuña-Parés, F., Dantignana, V., Oloo, W. N., Castillo, E., Draksharapu, A., Whiteoak, C. J., Martin-Diaconescu, V., Basallote, M. G., Luis, J. M., Que, L., Costas, M., & Company, A. (2018). Acid-Triggered O−O Bond Heterolysis of a Nonheme Fe^III(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds. Chemistry - A European Journal, 24(20), 5331-5340. https://doi.org/10.1002/chem.201704851

Serrano-Plana, J, Acuña-Parés, F, Dantignana, V, Oloo, WN, Castillo, E, Draksharapu, A, Whiteoak, CJ, Martin-Diaconescu, V, Basallote, MG, Luis, JM, Que, L, Costas, M & Company, A 2018, 'Acid-Triggered O−O Bond Heterolysis of a Nonheme Fe^III(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds', Chemistry - A European Journal, vol. 24, no. 20, pp. 5331-5340. https://doi.org/10.1002/chem.201704851

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title = "Acid-Triggered O−O Bond Heterolysis of a Nonheme FeIII(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds",

abstract = "A novel hydroperoxoiron(III) species [FeIII(OOH)(MeCN)(PyNMe3)]2+ (3) has been generated by reaction of its ferrous precursor [FeII(CF3SO3)2(PyNMe3)] (1) with hydrogen peroxide at low temperatures. This species has been characterized by several spectroscopic techniques and cryospray mass spectrometry. Similar to most of the previously described low-spin hydroperoxoiron(III) compounds, 3 behaves as a sluggish oxidant and it is not kinetically competent for breaking weak C−H bonds. However, triflic acid addition to 3 causes its transformation into a much more reactive compound towards organic substrates that is capable of oxidizing unactivated C−H bonds with high stereospecificity. Stopped-flow kinetic analyses and theoretical studies provide a rationale for the observed chemistry, a triflic-acid-assisted heterolytic cleavage of the O−O bond to form a putative strongly oxidizing oxoiron(V) species. This mechanism is reminiscent to that observed in heme systems, where protonation of the hydroperoxo intermediate leads to the formation of the high-valent [(Porph.)FeIV(O)] (Compound I).",

keywords = "C−H bond activation, density functional calculations, hydroperoxoiron(III), oxidation, stereospecific",

author = "Joan Serrano-Plana and Ferran Acu{\~n}a-Par{\'e}s and Valeria Dantignana and Oloo, {Williamson N.} and Esther Castillo and Apparao Draksharapu and Whiteoak, {Christopher J.} and Vlad Martin-Diaconescu and Basallote, {Manuel G.} and Luis, {Josep M.} and Lawrence Que and Miquel Costas and Anna Company",

note = "Funding Information: Financial support for this work was provided by the European Commission (2011-CIG-303522 to A.C., 675020-MSCA-ITN-2015-ETN to M.C.), the Spanish Ministry of Science (CTQ2015-70795-P to M.C., CTQ2016-77989-P to A.C., CTQ2014-52525-P to J.M.L., CTQ2015-65707-C2-2-P to M.G.B., and CSD2010-00065 to M.C and M.G.B.) and Generalitat de Catalunya (ICREA Academia Award to M.C. and 2014 SGR 862). The Spanish Ministry of Science is also acknowledged for a Ram{\'o}n y Cajal contract to A.C. (RYC-2011–08683). The work conducted at the University of Minnesota has been supported by the US National Science Foundation (grant CHE1665391 to L.Q.). XAS data was collected at the SOLEIL synchrotron SAMBA beamline (proposal 20150413). We would like to thank the beamline staff for their help with experiment preparation in particular Dr. Andrea Zitolo. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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T1 - Acid-Triggered O−O Bond Heterolysis of a Nonheme FeIII(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds

AU - Serrano-Plana, Joan

AU - Acuña-Parés, Ferran

AU - Dantignana, Valeria

AU - Oloo, Williamson N.

AU - Castillo, Esther

AU - Draksharapu, Apparao

AU - Whiteoak, Christopher J.

AU - Martin-Diaconescu, Vlad

AU - Basallote, Manuel G.

AU - Luis, Josep M.

AU - Que, Lawrence

AU - Costas, Miquel

AU - Company, Anna

N1 - Funding Information: Financial support for this work was provided by the European Commission (2011-CIG-303522 to A.C., 675020-MSCA-ITN-2015-ETN to M.C.), the Spanish Ministry of Science (CTQ2015-70795-P to M.C., CTQ2016-77989-P to A.C., CTQ2014-52525-P to J.M.L., CTQ2015-65707-C2-2-P to M.G.B., and CSD2010-00065 to M.C and M.G.B.) and Generalitat de Catalunya (ICREA Academia Award to M.C. and 2014 SGR 862). The Spanish Ministry of Science is also acknowledged for a Ramón y Cajal contract to A.C. (RYC-2011–08683). The work conducted at the University of Minnesota has been supported by the US National Science Foundation (grant CHE1665391 to L.Q.). XAS data was collected at the SOLEIL synchrotron SAMBA beamline (proposal 20150413). We would like to thank the beamline staff for their help with experiment preparation in particular Dr. Andrea Zitolo. Publisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/4/6

Y1 - 2018/4/6

N2 - A novel hydroperoxoiron(III) species [FeIII(OOH)(MeCN)(PyNMe3)]2+ (3) has been generated by reaction of its ferrous precursor [FeII(CF3SO3)2(PyNMe3)] (1) with hydrogen peroxide at low temperatures. This species has been characterized by several spectroscopic techniques and cryospray mass spectrometry. Similar to most of the previously described low-spin hydroperoxoiron(III) compounds, 3 behaves as a sluggish oxidant and it is not kinetically competent for breaking weak C−H bonds. However, triflic acid addition to 3 causes its transformation into a much more reactive compound towards organic substrates that is capable of oxidizing unactivated C−H bonds with high stereospecificity. Stopped-flow kinetic analyses and theoretical studies provide a rationale for the observed chemistry, a triflic-acid-assisted heterolytic cleavage of the O−O bond to form a putative strongly oxidizing oxoiron(V) species. This mechanism is reminiscent to that observed in heme systems, where protonation of the hydroperoxo intermediate leads to the formation of the high-valent [(Porph.)FeIV(O)] (Compound I).

AB - A novel hydroperoxoiron(III) species [FeIII(OOH)(MeCN)(PyNMe3)]2+ (3) has been generated by reaction of its ferrous precursor [FeII(CF3SO3)2(PyNMe3)] (1) with hydrogen peroxide at low temperatures. This species has been characterized by several spectroscopic techniques and cryospray mass spectrometry. Similar to most of the previously described low-spin hydroperoxoiron(III) compounds, 3 behaves as a sluggish oxidant and it is not kinetically competent for breaking weak C−H bonds. However, triflic acid addition to 3 causes its transformation into a much more reactive compound towards organic substrates that is capable of oxidizing unactivated C−H bonds with high stereospecificity. Stopped-flow kinetic analyses and theoretical studies provide a rationale for the observed chemistry, a triflic-acid-assisted heterolytic cleavage of the O−O bond to form a putative strongly oxidizing oxoiron(V) species. This mechanism is reminiscent to that observed in heme systems, where protonation of the hydroperoxo intermediate leads to the formation of the high-valent [(Porph.)FeIV(O)] (Compound I).

KW - C−H bond activation

KW - density functional calculations

KW - hydroperoxoiron(III)

KW - oxidation

KW - stereospecific

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