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 Acuna-Pares; 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 Acuna-Pares
, 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

Institut de Química Computacional i Catàlisi (IQCC)
Barcelona Institute of Science & Technology
University of Minnesota System
Universidad de Cadiz

Research output: Contribution to journal › Scientific article › peer-review

50 Citations (Scopus)

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
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
Publication status	Published - 6 Apr 2018

Keywords

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

Access to Document

10.1002/chem.201704851

http://hdl.handle.net/10256/15477Licence: Other

Cite this

Serrano-Plana, J., Acuna-Pares, 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

@article{7650414da258418296e8692bd0fc9a29,

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 Acuna-Pares 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 = "Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2018",

month = apr,

day = "6",

doi = "10.1002/chem.201704851",

language = "English",

volume = "24",

pages = "5331--5340",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley \& Sons",

number = "20",

}

Serrano-Plana, J, Acuna-Pares, 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

TY - JOUR

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 - Acuna-Pares, 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

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

UR - https://www.scopus.com/pages/publications/85040573297

U2 - 10.1002/chem.201704851

DO - 10.1002/chem.201704851

M3 - Scientific article

C2 - 29193378

AN - SCOPUS:85040573297

SN - 0947-6539

VL - 24

SP - 5331

EP - 5340

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 20

ER -

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

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this