title: Oxidative dehydrogenation of an amine group of a macrocyclic ligand in the coordination sphere of a Cu(II) complex.
abstract: The spontaneous oxidation of an amine group to an imine has been observed experimentally in an octa-aza macrocyclic dinucleating ligand LH(4) coordinated to Cu(II). The reaction is bimolecular and spontaneous in which amine groups of one macrocycle are oxidised and the Cu(II) centres of a second macrocyclic complex are reduced. No additional oxidating or external base agents are required. DFT calculations are carried out to compare the reaction with that recently reported for a ligand coordinated to an Fe(III) centre, but which requires an external base as proton acceptor. The computational results show that the copper and iron catalysed amine to imine reactions proceed via different mechanisms.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Avgda. Països Catalans 16, 43007 Tarragona, Catalonia, Spain.
authors.forename: Gemma J
authors.initials: GJ
authors.lastname: Christian
authors.forename: Arnau
authors.initials: A
authors.lastname: Arbuse
authors.forename: Xavier
authors.initials: X
authors.lastname: Fontrodona
authors.forename: Ma Angeles
authors.initials: MA
authors.lastname: Martinez
authors.forename: Antoni
authors.initials: A
authors.lastname: Llobet
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras
mesh_terms: D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry; D008024:Ligands; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D013816:Thermodynamics
chemical_list: D000588:Amines; D008024:Ligands; D003300:Copper; D007501:Iron