| Abstract |
The reactions of Cu-II carboxylates (valerate, 2-methylbutyrate, hexanoate, heptanoate) with pyrazole (Hpz) in EtOH or EtOH/water solutions easily afford the triangular trinuclear copper derivatives [Cu-3(mu(3)-OH)(mu-pz)(3)(RCOO)(2)(L)(x)] [R = CH3(CH2)(3) L = H2O, X = 1 for 5; R CH3CH2CH(CH3), L = EtOH, x = 2 for 6; R = CH3(CH2)4, L EtOH, x = 1 for 7; R = CH3(CH2)5, L = EtOH, x = 1 for 8] as it has been previously found for R = H, L = Hpz, x = 2, (1); R = CH3, L = Hpz, x = 1, (2); R = CH3CH2, L = EtOH, x = 1, (3) and [Cu-3(mu(3)-OH)(mu-pz)(3)-(CH3(CH2)(2)COO)(2)(MeOH)(H2O)], (4). The trinuclear structure common to 5-8 has been assigned on the basis of magnetic susceptibility studies, ESI MS, IR and UV/Vis spectroscopy as well as H-1 NMR measurements. The room temp. magnetic susceptibilities of 5-8 almost correspond to the presence of a single unpaired electron for each trinuclear unit. The IR spectra exhibit signals due to the bridging mu(3)-OH in accordance with what was observed in the spectra of 1-4. Solid-state and MeOH solution UV/Vis spectra show the same features previously reported for 1-4 and H-1 NMR spectra of 1-8 show almost identical low field signals that can be assigned to pz(-) hydrogens. A detailed investigation of the supramolecular structures of 1 and 4 and the single-crystal X-ray study of the polymeric paddlewheel Cu(2-methylbutyrate)(2), A, are also reported. Electrochemical experiments show that in 1-8 the Cu-II ions can be reduced, in distinct steps, to Cu-I and Cu-o. All the complexes act as catalysts or catalyst precursors for the efficient peroxidative oxidation, by aqueous hydrogen peroxide in acetonitrile and at room temp., of cycloalkanes RH (cyclohexane and cyclopentane) to the corresponding cyclic alcohols and ketones, with overall yields of up to 34\% and TONs up to 42. Radical pathways involving the formation of alkyl hydroperoxides (ROOH) are involved. ((C) Wiley-VCH Verlag GmbH \& Co. KGaA, 69451 Weinheim, Germany, 2009) |
