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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 CuI/CuII has been detected. Instead, the role of TEMPO is postulated to be the stabilization of a (bpy)(NMI)CuII‐O2??‐TEMPO (bpy=2,2′‐bipyridine, NMI=N‐methylimidazole) intermediate formed by electron transfer from CuI to molecular O2.  相似文献   

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