Characterization and Subsequent Reactivity of an Fe-Peroxo Porphyrin Generated by Electrochemical Reductive Activation of O2

Raquel Oliveira; Wiem Zouari; Christian Herrero; Frédéric Banse; Bernd Schöllhorn; Claire Fave; Elodie Anxolabéhère-Mallart

doi:10.1021/acs.inorgchem.6b01804

Characterization and Subsequent Reactivity of an Fe-Peroxo Porphyrin Generated by Electrochemical Reductive Activation of O₂

Inorg Chem. 2016 Dec 5;55(23):12204-12210. doi: 10.1021/acs.inorgchem.6b01804. Epub 2016 Nov 22.

Authors

Raquel Oliveira¹, Wiem Zouari¹, Christian Herrero², Frédéric Banse², Bernd Schöllhorn¹, Claire Fave¹, Elodie Anxolabéhère-Mallart¹

Affiliations

¹ Laboratoire d'Electrochimie Moléculaire, Université Paris Diderot, Université Sorbonne Paris Cité, UMR CNRS 7591 , 75205 PARIS Cedex 13, France.
² Institut de Chimie Moléculaire et des Matériaux d'Orsay, Université Paris Sud, Université Paris Saclay, UMR CNRS 8182 , 91405 Orsay Cedex, France.

PMID: 27934428
DOI: 10.1021/acs.inorgchem.6b01804

Abstract

Reductive activation of O₂ is achieved by using the [Fe^III(F₂₀TPP)Cl] (F₂₀TPP = 5,10,15,20-tetrakis(pentafluorophenyl) porphyrinate) porphyrin through electrochemical reduction of the [Fe^III(F₂₀TPP)(O₂^•-)] superoxo complex. Formation of the [Fe^III(F₂₀TPP)(OO)]^- peroxo species is monitored by using low-temperature electronic absorption spectroscopy, electron paramagnetic resonance, and cyclic voltammetry. Its subsequent protonation to yield the [Fe^III(F₂₀TPP)(OOH)] hydroperoxo intermediate is probed using low-temperature electronic absorption spectroscopy and electron paramagnetic resonance.