Self-assembled dicopper(II) diethanolaminate cores for mild aerobic and peroxidative oxidation of alcohols

The new dicopper(II) complexes [Cu-2(mu-Hmdea)(2)(NCS)(2)] (1) and [Cu-2(mu-Hedea)(2)(N-3)(2)]center dot(H2O)(0.25) (2) with the {Cu-2(mu-O)(2)} diethanolaminate cores have been easily generated by aqueous medium self-assembly reactions of copper(II) nitrate with N-methyl- or N-ethyldiethanolamine (H(2)mdea or H(2)edea, respectively), in the presence of sodium thiocyanate (for 1) or sodium azide (for 2) as ancillary ligands sources. They have been isolated as air-stable crystalline solids and fully characterized by IR and UV-vis spectroscopies, ESI-MS(+), elemental and single-crystal X-ray diffraction analyses. The latter complex also features a fourfold linkage of neighbouring dimeric units via strong intermolecular O-H center dot center dot center dot O hydrogen bonds, giving rise to the formation of tetracopper aggregates. The catalytic activity of compounds 1 and 2 has been studied for the mild (50-80 degrees C) and selective oxidations of alcohols, namely for (i) the aerobic aqueous medium oxidation of benzyl alcohols to benzaldehydes, mediated by TEMPO radical, and for (ii) the solvent-free oxidation of secondary alcohols to ketones by t-BuOOH under microwave (MW) irradiation. Complex 2 shows the highest efficiency in both oxidation systems, resulting in up to 99% molar yields (based on the alcohol substrate) of products. In addition, remarkably high values of TON (1020) and TOF (4080 h(-1)) have been achieved in the MW-assisted peroxidative oxidation of 1-phenylethanol to acetophenone (model reaction). Attractive green features of these catalytic systems include the operation in aqueous or solvent-free reaction medium, under mild conditions and with high yields and selectivities, using Cu catalyst precursors that are readily available by self-assembly in water of simple chemicals.