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

Juan Chen

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

Vertaalde titel van de bijdrage: Mechanismes in niet-heem-ijzeroxidatie katalyse: Fotochemie en waterstofperoxide activatie

Juan Chen

Moleculaire Anorganische Chemie

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In dit proefschrift focussen we voornamelijk op de fotoactivatie van niet-heem ijzercomplexen en de mechanismen van thermische reacties van niet-heem
ijzercomplexen met H2O2. Hoofdstukken 2, 3 en 4 focussen op de fotochemische activatie van ijzercomplexen in de Fe(IV)- en Fe(II)oxidatietoestanden.
In hoofdstuk 2 worden de activatie van niet-heem ijzer(IV)-oxo-complexen en de bijbehorende mechanismen onderzocht. In hoofdstuk 3 laat de aerobe
fotokatalytische oxidatie van methanol zien dat het fotoactieve niet-heem -oxo-di-ijzercomplex een rol speelt in het mechanisme van
fotodisproportionering van het di-ijzer(III)complex. In hoofdstuk 4 wordt de oxidatieve fotodegradatie van niet-heem ijzer-polypyridyl-complexen onder
basische omstandigheden onderzocht, en worden de implicaties van de getrokken conclusies met betrekking tot ligandontwerp bediscussieerd.
Hoofdstukken 5 en 6 focussen op het mechanisme van thermische generatie van hoogvalente ijzer(IV)-oxo-complexen door reactie van
niet-heem ijzer(III) met H2O2. In hoofdstuk 5 wordt gefocust op de vorming van hoogvalente ijzer(IV)-oxo-complexen via de heterolyse van
een O-O binding in een Fe(II)-OOH-complex. Dit Fe(II)-complex werd gevormd met een stoichiometrische hoeveelheid H2O2. In hoofdstuk 6 wordt een
nieuwe mechanistische route gedemonstreerd voor de reactie van Fe(III)OOH-complexen met H2O2. Deze route is kinetisch gunstiger dan de
homolytische scheiding van de Fe(III)OOH O-O binding, waarbij hoogvalente ijzer(IV)-oxo-complexen ontstaan. Er wordt gedemonstreerd dat de
beschreven mechanistische routes nadelig zijn voor de katalytische oxidatie van organische substraten.

Vertaalde titel van de bijdrage	Mechanismes in niet-heem-ijzeroxidatie katalyse: Fotochemie en waterstofperoxide activatie
Originele taal-2	English
Kwalificatie	Doctor of Philosophy
Toekennende instantie	Rijksuniversiteit Groningen
Begeleider(s)/adviseur	Browne, Wesley, Supervisor Otten, Edwin, Supervisor
Datum van toekenning	15-jun.-2018
Plaats van publicatie	[Groningen]
Uitgever	University of Groningen
Gedrukte ISBN's	978-94-034-0731-9
Elektronische ISBN's	978-94-034-0730-2
Status	Published - 2018

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Title and contentsFinal publisher's version, 603 KB
Chapter 1Final publisher's version, 2,3 MB
Chapter 2Final publisher's version, 2,13 MB
Chapter 3Final publisher's version, 2,24 MB
Chapter 4Final publisher's version, 2,1 MB
Chapter 5Final publisher's version, 2,54 MB
Chapter 6Final publisher's version, 2,11 MB
AppendixFinal publisher's version, 584 KB
Complete thesisFinal publisher's version, 11,4 MB
PropositionsFinal publisher's version, 296 KB

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@phdthesis{15a3c2a4b8154bc29c829f80b9695de6,

title = "Mechanisms in non-heme iron oxidation catalysis: Photochemistry and hydrogen peroxide activation",

abstract = "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.",

author = "Juan Chen",

year = "2018",

language = "English",

isbn = "978-94-034-0731-9",

publisher = "University of Groningen",

school = "University of Groningen",

}

TY - BOOK

T1 - Mechanisms in non-heme iron oxidation catalysis

T2 - Photochemistry and hydrogen peroxide activation

AU - Chen, Juan

PY - 2018

Y1 - 2018

N2 - 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.

AB - 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.

M3 - Thesis fully internal (DIV)

SN - 978-94-034-0731-9

PB - University of Groningen

CY - [Groningen]

ER -

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

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