New insights into the electronic structure and reactivity of one-electron oxidized copper(II)-(disalicylidene)diamine complexes.

The neutral and one-electron oxidized Cu(II) six-membered chelate 1,3-Salcn (1,3-Salcn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-cyclohexanediamine) complexes have been investigated and compared with the five-membered chelate 1,2-Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) complexes. Cyclic voltammetry of Cu(1,3-Salcn) showed two reversible redox waves at 0.48 and 0.68 V, which are only 0.03 V higher than those of Cu(1,2-Salcn). Reaction of Cu(1,3-Salcn) with 1 equiv of AgSbF6 afforded the oxidized complex which exists as a ligand-based radical species in solution and in the solid state. The X-ray crystal structure of the oxidized complex, [Cu(1,3-Salcn)]SbF6, exhibited an asymmetric metal binding environment with a longer Cu-O bond and quinoid distortion in the phenolate moiety on one side, demonstrating at least partial ligand radical localization in the solid state. The ligand oxidation is also supported by XPS and temperature dependent magnetic susceptibility. The electronic structure of the [Cu(1,3-Salcn)](+) complex was further probed by UV-vis-NIR, resonance Raman, and electron paramagnetic resonance (EPR) measurements, and by theoretical calculations, indicating that the phenoxyl radical electron is relatively localized on one phenolate moiety in the molecule. The reactivity of [Cu(1,3-Salcn)](+) with benzyl alcohol was also studied. Quantitative conversion of benzyl alcohol to benzaldehyde was observed, with a faster reaction rate in comparison with [Cu(1,2-Salcn)](+). The kinetic isotope effect (KIE = k(H)/k(D)) of benzyl alcohol oxidation by [Cu(1,3-Salcn)](+) was estimated to be 13, which is smaller than the value reported for [Cu(1,2-Salcn)](+). The activation energy difference between [Cu(1,2-Salcn)](+) and [Cu(1,3-Salcn)](+) was in good agreement with the energy calculated from KIE. This correlation suggests that the Cu(II)-phenoxyl radical species, characterized for [Cu(1,2-salcn)](+) is more reactive for hydrogen abstraction from benzyl alcohol in comparison to the 1:1 mixture of Cu(III)-phenolate and Cu(II)-phenoxyl radical species, [Cu(1,2-Salcn)](+). Thus, the Cu(II)-phenoxyl radical species accelerates benzyl alcohol oxidation in comparison with the Cu(III)-phenolate ground state complex, in spite of the similar activated intermediate and oxidation pathway.

Characterization of one-electron oxidized copper(II)-salophen-type complexes; effects of electronic and geometrical structures on reactivities.

One-electron oxidized salophen-type complexes, [Cu(salophen)](+) (H2salophen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminobenzene), and its methoxy derivatives, [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), have been synthesized and structurally characterized, and their reactivities have been investigated. The solid state structures of the one-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. On the other hand, [Cu(salophen)](+) in solution 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 alcohol has been investigated in the presence of a large excess of substrate, which revealed the difference in the kinetic behavior between the complexes. The mechanisms of the oxidation have been discussed on the basis of the electronic and geometrical structures and the reaction kinetics.