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

Research output: Contribution to journalArticle

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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).

LanguageEnglish (US)
Pages5331-5340
Number of pages10
JournalChemistry - A European Journal
Volume24
Issue number20
DOIs
StatePublished - Apr 6 2018

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Hydroxylation
Acids
Protonation
Heme
Organic compounds
Oxidants
Hydrogen Peroxide
Mass spectrometry
Kinetics
Substrates
Temperature
trifluoromethanesulfonic acid

Keywords

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

Cite this

Serrano-Plana, J., Acuña-Parés, F., Dantignana, V., Oloo, W. N., Castillo, E., Draksharapu, A., ... Company, A. (2018). Acid-Triggered O−O Bond Heterolysis of a Nonheme FeIII(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds. Chemistry - A European Journal, 24(20), 5331-5340. DOI: 10.1002/chem.201704851

Acid-Triggered O−O Bond Heterolysis of a Nonheme FeIII(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds. / Serrano-Plana, Joan; Acuña-Parés, Ferran; Dantignana, Valeria; Oloo, Williamson N.; Castillo, Esther; Draksharapu, Apparao; Whiteoak, Christopher J.; Martin-Diaconescu, Vlad; Basallote, Manuel G.; Luis, Josep M.; Que, Lawrence; Costas, Miquel; Company, Anna.

In: Chemistry - A European Journal, Vol. 24, No. 20, 06.04.2018, p. 5331-5340.

Research output: Contribution to journalArticle

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 FeIII(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds' Chemistry - A European Journal, vol 24, no. 20, pp. 5331-5340. DOI: 10.1002/chem.201704851
Serrano-Plana, Joan ; Acuña-Parés, Ferran ; Dantignana, Valeria ; Oloo, Williamson N. ; Castillo, Esther ; Draksharapu, Apparao ; Whiteoak, Christopher J. ; Martin-Diaconescu, Vlad ; Basallote, Manuel G. ; Luis, Josep M. ; Que, Lawrence ; Costas, Miquel ; Company, Anna. / Acid-Triggered O−O Bond Heterolysis of a Nonheme FeIII(OOH) Species for the Stereospecific Hydroxylation of Strong C−H Bonds. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 20. pp. 5331-5340
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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).",
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