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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
Journal of Molecular Catalysis A: Chemical Pub Date : 2016-09-05 , DOI: 10.1016/j.molcata.2016.09.005
Oksana V. Nesterova , Dmytro S. Nesterov , Agnieszka Krogul-Sobczak , M. Fátima C. Guedes da Silva , Armando J.L. Pombeiro

The complexes of copper [Cu(κONN’-HL)(NO3)(DMF)](NO3)∙H2O (1) and [Cu(κONN’-HL)Cl2]∙½DMSO (2), and of manganese [Mn(κON-HL)2Cl2]Cl (3) and [Mn(κON-HL)2(NO3)2](NO3)∙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 1 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.



中文翻译:

Cu(II)和Mn(III)Schiff碱配合物的合成,晶体结构和催化活性:添加剂对环己烷和1-苯基乙醇的氧化催化的影响

铜的配合物[铜(κ ONN '-HL)(NO 3)(DMF)](NO 3)∙ħ 2 O(1)和[铜(κ ONN ' -HL)氯2 ]∙½DMSO(2)和锰的[锰(κ ON -HL)22 ]氯(3)和[锰(κ ON -HL)2(NO 32 ](NO 3)∙ħ 2 O(4通过各自的氯化物或硝酸盐与席夫碱氨基醇HL(水杨醛与氨乙基哌嗪的缩合产物)的非水溶液反应合成),并通过X射线衍射分析进行表征。催化研究表明,铜化合物12具有显着活性在温和的条件下,在各种促进剂(硝酸,盐酸,草酸和吡啶)存在下,用过氧化氢氧化环己烷。吡啶对铜催化剂催化活性的不同寻常的促进作用使基于环己烷的收率最高达到21%。色谱研究表明,环己基过氧化氢是主要反应产物,还检测到了氯环己烷(在盐酸作为促进剂的情况下),这表明自由基反应途径以羟基自由基为攻击物种。配合物12叔丁基氧化1-苯乙醇中也起催化剂的作用-丁基过氧化氢,在K 2 CO 3启动子存在下,苯乙酮的收率高达62%,TON(周转数)高达620 。

更新日期:2016-09-05
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