Mechanisms in non-heme iron oxidation catalysis: Photochemistry and hydrogen peroxide activation

Juan Chen

Research output: ThesisThesis fully internal (DIV)

745 Downloads (Pure)


In this thesis, we focus mainly on the photo activation non-heme iron complexes, as well as mechanisms of thermal reactions of non-heme iron complex with H2O2.
Chapter 2, 3 and 4, focus on photochemically induced activation of iron complexes in the Fe(IV) and Fe(III) oxidation states.In chapter 2, the direct activation of non-heme iron(IV)-oxo complexes and the mechanisms involved are explored. In chapter 3 the photo-catalytic oxidation of methanol under aerobic
conditions reveals the involvement of a photo-active non-heme miu-oxo bridged diiron(III) complex and its mechanism for photo-induced
disproportionation. In chapter 4, the photo-induced oxidative degradation of the non-heme iron polypyridyl complexes under basic conditions are explored
and the implications the conclusions reached hold in regard to ligand design is discussed. Chapters 5 and 6 focus on the mechanism of thermal generation
of high-valent iron(IV)-oxo complexes by reaction of non-heme iron(II) complexes with H2O2. In chapter 5, the generation of an iron(IV)-oxo complex via heterolysis of an O-O bond in an Fe(III)-OOH species formed with stoichiometric H2O2 is focused on. In chapter 6, a novel reaction pathway for the reaction of iron(III)-hydroperoxo species with H2O2 is established. This pathway is kinetically favored compared to the homolytic cleavage of the O-O bond in
Fe(III)OOH, which would form high-valent iron(IV)-oxo species. The reaction pathways described are shown to be detrimental to the efficiency of the
complexes in the catalytic oxidation of organic substrates.
Translated title of the contributionMechanismes in niet-heem-ijzeroxidatie katalyse: Fotochemie en waterstofperoxide activatie
Original languageEnglish
QualificationDoctor of Philosophy
Awarding Institution
  • University of Groningen
  • Browne, Wesley, Supervisor
  • Otten, Edwin, Supervisor
Award date15-Jun-2018
Place of Publication[Groningen]
Print ISBNs978-94-034-0731-9
Electronic ISBNs978-94-034-0730-2
Publication statusPublished - 2018

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