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3721334 
Journal Article 
Synthesis, crystal structures and catalytic activity of Cu(II) and Mn(III) Schiff base complexes: Influence of additives on the oxidation catalysis of cyclohexane and 1-phenylehanol 
Nesterova, OV; Nesterov, DS; Krogul-Sobczak, A; Guedes da Silva, MFC; Pombeiro, AJL 
2017 
Yes 
Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169 
426 
506-515 
WOS:000391075700028 
The complexes of copper [Cu(kappa ONN'-HL)(NO3)(DMF)](NO3)center dot H2O (1) and [Cu(kappa ONN'-HL)CL2]center dot 1/2DMSO (2), and of manganese [Mn(kappa ON-HL)(2)Cl-2]Cl (3) and [Mn(kappa ON-HL)(2)(NO3)(2)](NO3)center dot H2O (4) were synthesized by reactions of the respective chloride or nitrate salt with a non-aqueous solutions of the Schiff base aminoalcohol HL (product of condensation of salicylic aldehyde and aminoethylpiperazine) and characterized by X-ray diffraction analysis. The catalytic investigations disclosed a prominent activity of the copper compounds 1 and 2 towards oxidation of cyclohexane with hydrogen peroxide in the presence of various promoters (nitric, hydrochloric, oxalic acids and pyridine), under mild conditions. The unusual promoting effect of pyridine on the catalytic activity of the copper catalysts allowed to achieve yields up to 21% based on cyclohexane. Chromatographic studies revealed that cyclohexyl hydroperoxide is a main reaction product and chlorocyclohexane (in the presence of HCl as promoter) was also detected, suggesting a free radical reaction pathway with hydroxyl radicals as attacking species. Complexes I and 2 act also as catalysts in the oxidation of 1-phenylethanol with tert-butylhydroperoxide, showing acetophenone yields up to 62% and TON (turnover numbers) up to 620 in the presence of the K2CO3 promoter. (C) 2016 Elsevier B.V. All rights reserved. 
Alkane oxidation; Alcohol oxidation; Hydrogen peroxide; Alkyl radical; Metal complex catalysis