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Reactivity of Copper(I) Complexes Containing Ligands Derived from (1 S ,3 R )‐Camphoric Acid with Dioxygen
Author(s) -
Stöhr Fabian,
Kulhanek Niclas,
Becker Jonathan,
Göttlich Richard,
Schindler Siegfried
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202100187
Subject(s) - chemistry , reactivity (psychology) , ligand (biochemistry) , copper , medicinal chemistry , pyridine , regioselectivity , benzaldehyde , hydroxylation , intramolecular force , amine gas treating , deprotonation , stereochemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology , ion , biochemistry , receptor , enzyme
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 (1 R , 3 S )‐ 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.