Amine derivatives prepared from camphoric acid were used as ligands for the synthesis of corresponding copper(I) complexes. Their reactivity towards dioxygen was analyzed. The formation of a short-lived bis(μ-oxido)copper complex was spectroscopically observed during the reaction of the copper(I) complex with (1R, 3S)-N 1 ,N 1 ,N 3 ,N 3 -Tetramethyl-1,2,2-trimethylcyclopentane-1,3-diamine as a ligand. Furthermore, a regioselective demethylation of the ligand system was detected.Deuteration of the methyl groups of the ligand allowed crystallization and characterization of the bis(μ-oxido)copper complex. Derivatives of the ligand with pyridine residues caused suppression of the reactivity of the corresponding copper(I) complexes towards dioxygen. Additionally, the ligand system could be modified for intramolecular oxygenation reactions with benzaldehyde that led to the formation of salicylaldehyde, a selective hydroxylation in ortho position.

The Front Cover shows the reaction of dioxygen with a copper(I) complex containing a tetramethylated diamine ligand that is related to camphor. The formation of a short‐lived bis(μ‐oxido) copper complex was observed spectroscopically by low temperature stopped‐flow kinetics. Deuteration of the methyl groups enabled crystallization and structural characterization of this reactive intermediate. More information can be found in the Full Paper by R. Göttlich, S. Schindler and co‐workers.