Structure-reactivity relationships in Cu/TEMPO catalyzed aerobic alcohol oxidation : mechanistic assessment by (coupled) operando spectroscopic tools

Sven Adomeit

doi:10.18453/rosdok_id00002740

Sven Adomeit

Structure-reactivity relationships in Cu/TEMPO catalyzed aerobic alcohol oxidation : mechanistic assessment by (coupled) operando spectroscopic tools

Universität Rostock, 2019

https://doi.org/10.18453/rosdok_id00002740

Abstract: Aerobic alcohol oxidation is a route to convert alcohols into aldehydes using homogenous Cu catalysts with O2 as the terminal oxidant. It is well-known that the Cu catalyst forms a Cu(I/II) shuttle during the reaction. To investigate still open issues coupled operando EPR/UV-vis/ATR-IR was used in a first step. Through this combination it was possible to observe distinctive effects of the structure and molar ratios of ligands/additives upon the redox behavior of the Cu(I/II) shuttle. The triple coupling was further developed into a 4-in-1 set-up by implementing X-ray absorption spectroscopy.

doctoral thesis free access

title:

Structure-reactivity relationships in Cu/TEMPO catalyzed aerobic alcohol oxidation: mechanistic assessment by (coupled) operando spectroscopic tools

contributing persons:

Sven Adomeit[VerfasserIn]
	1191927156
Angelika Brückner[AkademischeR BetreuerIn]
	14344526X
Felix Tuczek[AkademischeR BetreuerIn]
	0000-0001-7290-9553
	1019185198

contributing corporate bodies:

Universität Rostock[Grad-verleihende Institution]
	38329-6
Universität Rostock, Mathematisch-Naturwissenschaftliche Fakultät[Grad-verleihende Institution]
	2147083-2

abstract:

Aerobic alcohol oxidation is a route to convert alcohols into aldehydes using homogenous Cu catalysts with O2 as the terminal oxidant. It is well-known that the Cu catalyst forms a Cu(I/II) shuttle during the reaction. To investigate still open issues coupled operando EPR/UV-vis/ATR-IR was used in a first step. Through this combination it was possible to observe distinctive effects of the structure and molar ratios of ligands/additives upon the redox behavior of the Cu(I/II) shuttle. The triple coupling was further developed into a 4-in-1 set-up by implementing X-ray absorption spectroscopy. [English]

Aerobe Alkoholoxidationen sind Synthesewege, die als Katalysatoren Kupfer-Komplexe sowie molekularen Sauerstoff als Oxidationsmittel verwenden. Während der Reaktion alterniert ein Cu-Komplex zwischen den Oxidationsstufen I und II. Zur genaueren Untersuchung wurde eine operando Kopplung aus EPR/UV-vis/ATR-IR angewendet, durch die ein deutlicher Einfluss der verschiedenen Liganden/Additive sowie deren Konzentration auf das Redoxverhalten des Cu(I/II) Shuttles aufgezeigt wurde. Es wurde zudem eine neuartige Kopplung aus EPR/UV-vis/ATR-IR und XAS entwickelt und zum weltweit ersten Mal getestet. [German]

document type:

doctoral thesis

institution:

Faculty of Mathematics and Natural Sciences

language:

English

subject class (DDC):

540 Chemistry & allied sciences

publication /
production:

Rostock

Rostock: Universität Rostock

2019

statement of responsibility:

vorgelegt von Sven Adomeit

notes:

GutacherInnen: Angelika Brückner (Universität Rostock, Leibniz-Institut für Katalyse e.V.) ; Felix Tuczek (Christian-Albrechts-Universität zu Kiel, Institut für Anorganische Chemie)

identifiers: