Département de chimie moléculaire

One-electron oxidized salophen-type complexes, [Cu(salophen)]+ (H2salophen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminobenzene), and its methoxy derivs., [Cu(MeO-salophen)]+ and [Cu(salophen-(MeO)2)]+ (H2MeO-salophen = N,N'-bis(3-tert-butyl-5-methoxysalicylidene)-1,2-diaminobenzene, H2salophen-(MeO)2 = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diamino-4,5-dimethoxybenzene), were synthesized and structurally characterized, and their reactivities were studied. The solid state structures of the 1-electron oxidized forms of these complexes suggested that [Cu(salophen)]+ and [Cu(MeO-salophen)]+ can be assigned to relatively localized Cu(II)-phenoxyl radical complexes, while [Cu(salophen-(MeO)2)]+ is the diiminobenzene radical complex. However, [Cu(salophen)]+ in soln. showed a different electronic structure from that of the solid sample, the radical electron being delocalized over the whole $π$-conjugated ligand. The reaction of these oxidized complexes with benzyl alc. was studied in the presence of a large excess of substrate, which revealed the difference in the kinetic behavior between the complexes. The mechanisms of the oxidn. are discussed from the electronic and geometrical structures and the reaction kinetics. [on SciFinder(R)]