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A new hexa-nuclear Cu(II) complex [Cu 3 (μ 2 -1κ NO 2  ,2κ NO 2  -L)(μ-Cl) 2 (Cl)(MeOH)(DMF) 2 ] 2 ( 1 ), where H 4 L = N' 1 ,N' 2  -bis(2-hydroxybenzylidene)oxalohydrazide, was synthesized and fully characterized by IR spectroscopy, ESI-MS, elemental analysis, and single crystal X-ray diffraction. Complex 1 and the dinuclear oxidovanadium(V) one [{VO(OEt)(EtOH)} 2 (1κ NO 2  ,2κ NO 2  -L)]·2H 2 O ( 2 ) were used as catalyst precursors for the neat oxidation of primary (cinnamyl alcohol) and secondary (1-phenyl ethanol, benzhydrol) benzyl alcohols and of the secondary aliphatic alcohol cyclohexanol, under microwave irradiation using tert -butyl hydroperoxide (TBHP) as oxidant. Oxidations proceed via radical mechanisms. The copper(II) compound 1 exhibited higher catalytic activity than the vanadium(V) complex 2 for all the tested alcohol substrates. The highest conversion was found for 1-phenylethanol, yielding 95.3% of acetophenone in the presence of 1 and in solvent and promoter-free conditions. This new Cu(II) complex was found to exhibit higher activity under milder reaction conditions than the reported aroylhydrazone Cu(II) analogues.

Aroylhydrazone Schiff Base Derived Cu(II) and V(V) Complexes: Efficient Catalysts towards Neat Microwave-Assisted Oxidation of Alcohols