NEW HEXAAZA MACROCYCLIC BINUCLEATING LIGANDS - OXYGEN INSERTION WITH A DICOPPER(I) SCHIFF-BASE MACROCYCLIC COMPLEX
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Direct 2:2 condensation of isophthalaldehyde with diethylenetriamine produces a hexaaza 24-membered macrocyclic tetra Schiff base in good yield. The crystal structure of an isomeric form of the Schiff base is reported. Crystal data for N6C24H30MeOH: C2/c,a = 17.283 (2) , b = 16.930 (2) , c = 17.953 (3) , = 118.73 (2), V= 4607 (2) 3, Z = 8, R(F) = 0.059 for 1538 observations (I > 3((I)) and 289 variables. The amber binuclear Cu(I) complex of the tetraaza macrocyclic Schiff base combines with a molar equivalent of dioxygen to form a green binuclear Cu(II) complex, which contains a bridging hydroxide ion and, by oxygen insertion, a bridging phenolate donor. These results provide the first macrocyclic tyrosinase model. Hydrogenation of the Schiff base provides the corresponding saturated hexaaza macrocyclic ligand. The protonation constants of the reduced macrocycle, as well as the binding constants of its mononuclear and binuclear Cu(Il) complexes, have been determined potentiometrically. 1990, American Chemical Society. All rights reserved.
author list (cited authors)
MENIF, R., MARTELL, A. E., SQUATTRITO, P. J., & CLEARFIELD, A.
complete list of authors
MENIF, R||MARTELL, AE||SQUATTRITO, PJ||CLEARFIELD, A