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

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SERRANO-PLANA, Joan, ACUÑA-PARÉS, Ferran, DANTIGNANA, Valeria, OLOO, Williamson N., CASTILLO, Esther, DRAKSHARAPU, Apparao, WHITEOAK, Christopher, MARTIN-DIACONESCU, Vlad, BASALLOTE, Manuel G., LUIS, Josep M., QUE, Lawrence, COSTAS, Miquel and COMPANY, Anna (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. [Article]

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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).

More Information

Official URL:

https://onlinelibrary.wiley.com/doi/abs/10.1002/ch...

Research Institute, Centre or Group - Does NOT include content added after October 2018:

Biomedical Research Centre

Departments - Does NOT include content added after October 2018:

Health and Well-being > Department of Bioscience

Page Range:

5331-5340

Identifiers

Identification Number:

10.1002/chem.201704851