COPPER-(I) AND COPPER-(II) COMPLEXES OF A MACROCYCLE DERIVED FROM 2 2CONDENSATION OF PYRIDINE-2,6-DICARBALDEHYDE AND 4-AZAHEPTANE-1,7-DIAMINE, OXYGENATION OF THE COPPER(I) COMPLEX/

A Schiff-base macrocycle was prepared by the 2:2 condensation of pyrid ine-2,6-dicarbaldehyde and 4-azaheptane-1,7-diamine. It crystallized i n the orthorhombic space group Fdd2 with a = 16.984(8), b = 31.322(12) , c = 11.026(6) Angstrom and Z = 16. This 20-membered ring-contracted form, with two Schiff-base double bonds, forms a deep red dinuclear co pper-(I) complex having two charge-transfer absorptions at 415 and 550 nm in methanol-acetonitrile (4:1). The complex forms a deep purple di copper-dioxygen complex having absorption bands at 390 and 530 nm, wit h a rate constant at 25.0 degrees C of 5.6 x 10(5) s(-1). This is spon taneously converted into a copper(II) complex with a half-life of 240 min. The dinuclear copper(I) dioxygen complex oxidizes 3,5-di-tert-but ylcatechol catalytically to 3,1-di-tert-butyl-1,2-benzoquinone. The di nuclear copper(I) complex of the macrocycle was also found to oxidize this substrate to the same product at a much faster rate.