Oksana V. Nesterova , Dmytro S. Nesterov , Agnieszka Krogul-Sobczak , M. Fátima C. Guedes da Silva , Armando J.L. Pombeiro
{"title":"Cu(II)和Mn(III)希夫碱配合物的合成、晶体结构和催化活性:添加剂对环己烷和1-苯乙醇氧化催化的影响","authors":"Oksana V. Nesterova , Dmytro S. Nesterov , Agnieszka Krogul-Sobczak , M. Fátima C. Guedes da Silva , Armando J.L. Pombeiro","doi":"10.1016/j.molcata.2016.09.005","DOIUrl":null,"url":null,"abstract":"<div><p>The complexes of copper [Cu(κ<em>ONN</em>’-HL)(NO<sub>3</sub>)(DMF)](NO<sub>3</sub>)∙H<sub>2</sub>O (<strong>1</strong>) and [Cu(κ<em>ONN</em>’-HL)Cl<sub>2</sub>]∙½DMSO (<strong>2</strong>), and of manganese [Mn(κ<em>ON</em>-HL)<sub>2</sub>Cl<sub>2</sub>]Cl (<strong>3</strong>) and [Mn(κ<em>ON</em>-HL)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>](NO<sub>3</sub>)∙H<sub>2</sub>O (<strong>4</strong>) 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 <strong>1</strong> and <strong>2</strong> 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 <strong>1</strong> and <strong>2</strong> act also as catalysts in the oxidation of 1-phenylethanol with <em>tert</em>-butylhydroperoxide, showing acetophenone yields up to 62% and TON (turnover numbers) up to 620 in the presence of the K<sub>2</sub>CO<sub>3</sub> promoter.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 506-515"},"PeriodicalIF":5.0620,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.09.005","citationCount":"39","resultStr":"{\"title\":\"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\",\"authors\":\"Oksana V. Nesterova , Dmytro S. Nesterov , Agnieszka Krogul-Sobczak , M. Fátima C. Guedes da Silva , Armando J.L. Pombeiro\",\"doi\":\"10.1016/j.molcata.2016.09.005\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The complexes of copper [Cu(κ<em>ONN</em>’-HL)(NO<sub>3</sub>)(DMF)](NO<sub>3</sub>)∙H<sub>2</sub>O (<strong>1</strong>) and [Cu(κ<em>ONN</em>’-HL)Cl<sub>2</sub>]∙½DMSO (<strong>2</strong>), and of manganese [Mn(κ<em>ON</em>-HL)<sub>2</sub>Cl<sub>2</sub>]Cl (<strong>3</strong>) and [Mn(κ<em>ON</em>-HL)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>](NO<sub>3</sub>)∙H<sub>2</sub>O (<strong>4</strong>) 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 <strong>1</strong> and <strong>2</strong> 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 <strong>1</strong> and <strong>2</strong> act also as catalysts in the oxidation of 1-phenylethanol with <em>tert</em>-butylhydroperoxide, showing acetophenone yields up to 62% and TON (turnover numbers) up to 620 in the presence of the K<sub>2</sub>CO<sub>3</sub> promoter.</p></div>\",\"PeriodicalId\":370,\"journal\":{\"name\":\"Journal of Molecular Catalysis A: Chemical\",\"volume\":\"426 \",\"pages\":\"Pages 506-515\"},\"PeriodicalIF\":5.0620,\"publicationDate\":\"2017-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/j.molcata.2016.09.005\",\"citationCount\":\"39\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Catalysis A: Chemical\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1381116916303776\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Catalysis A: Chemical","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1381116916303776","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
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
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.
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The Journal of Molecular Catalysis A: Chemical publishes original, rigorous, and scholarly full papers that examine the molecular and atomic aspects of catalytic activation and reaction mechanisms in homogeneous catalysis, heterogeneous catalysis (including supported organometallic catalysis), and computational catalysis.
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