Selective Alcohol Oxidation by a Copper-TEMPO Catalyst: Mechanistic Insights by Simultaneously Coupled Operando EPR/UV-Vis/ATR-IR Spectroscopy
Dr. Jabor Rabeah 1,* , Dr. Ursula Bentrup 1,* , Prof. Dr. Reinhard Stößer 2 and Prof. Dr. Angelika Brückner 1,* 1 .Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock (Germany) 2 .Institut für Chemie-Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin-Adlershof (Germany) Article first published online: 14 JUL 2015 DOI: 10.1002/anie.201504813 Abstract 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) intermedia...