Selective Alcohol Oxidation by a Copper TEMPO Catalyst: Mechanistic Insights by Simultaneously Coupled Operando EPR/UV‐Vis/ATR‐IR Spectroscopy | Zendy

Rabeah Jabor | Zendy; Bentrup Ursula | Zendy; Stößer Reinhard | Zendy; Brückner Angelika | Zendy

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Selective Alcohol Oxidation by a Copper TEMPO Catalyst: Mechanistic Insights by Simultaneously Coupled Operando EPR/UV‐Vis/ATR‐IR Spectroscopy

Author(s) -

Rabeah Jabor,

Bentrup Ursula,

Stößer Reinhard,

Brückner Angelika

Publication year - 2015

Publication title -

angewandte chemie international edition

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 5.831

H-Index - 550

eISSN - 1521-3773

pISSN - 1433-7851

DOI - 10.1002/anie.201504813

Subject(s) - electron paramagnetic resonance , copper , catalysis , chemistry , benzyl alcohol , alcohol , redox , photochemistry , alcohol oxidation , spectroscopy , infrared spectroscopy , ultraviolet visible spectroscopy , electron transfer , inorganic chemistry , organic chemistry , nuclear magnetic resonance , physics , quantum mechanics

The first coupled operando EPR/UV‐Vis/ATR‐IR spectroscopy setup for mechanistic studies of gas‐liquid phase reactions is presented and exemplarily applied to the well‐known copper/TEMPO‐catalyzed (TEMPO=(2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl) oxidation of benzyl alcohol. In contrast to previous proposals, no direct redox reaction between TEMPO and Cu I /Cu II has been detected. Instead, the role of TEMPO is postulated to be the stabilization of a (bpy)(NMI)Cu II ‐O 2 ⋅− ‐TEMPO (bpy=2,2′‐bipyridine, NMI= N ‐methylimidazole) intermediate formed by electron transfer from Cu I to molecular O 2 .

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