{"title":"壳聚糖基铁(III)和镍(II)催化剂上的 C-H 键活化","authors":"Neha Tiwari , Charvi Pandey , Jagat Singh Kirar , Savita Khare","doi":"10.1016/j.jics.2024.101395","DOIUrl":null,"url":null,"abstract":"<div><div>Chitosan (Cs) supported heterogeneous catalysts of Fe(III) and Ni(II) is developed by the equimolar reaction of two schiff base ligands, L<sub>1</sub> [Cs-HACP] and L<sub>2</sub> [ANI-HACP] and Metal salts {where Metal = Fe(III) and Ni(II)}with chitosan. The L<sub>1</sub> ligand is prepared by the reaction of chitosan (Cs) and ortho hydroxyl (HACP) acetophenone in methanol and L<sub>2</sub> ligand is prepared by the condensation of aniline (ANI) and ortho hydroxyl acetophenone (HACP) in solvent free condition. The prepared catalysts {M-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>} are characterized by different analytical techniques viz. scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), powder X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), Raman, UV-VIS-NIR, X-ray photoelectron spectroscopy (XPS) and computational studies. The catalytic behavior of newly synthesized catalysts are tested for the C–H activation using 70 % <em>tert</em>-butyl hydroperoxide (TBHP). The best results are obtained for tetralin oxidation. The order of catalytic reactivity of {M-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>}catalyst is in decreasing order: {Fe(III)-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>} > {Ni(II)-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>}. The {Fe(III)-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>} gives maximum conversion 81.99 % of tetralin with 84.50 % selectivity of tetralone (T-lone) and 6.47 % selectivity of tetralol (T-lol) after 5 h of reaction at 80 °C temperature. The chitosan based heterogeneous catalyst is easy to separate and recover. It can be recycled seven times.</div></div>","PeriodicalId":17276,"journal":{"name":"Journal of the Indian Chemical Society","volume":"101 11","pages":"Article 101395"},"PeriodicalIF":3.2000,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"C–H bond activation over chitosan based Fe(III) and Ni(II) catalysts\",\"authors\":\"Neha Tiwari , Charvi Pandey , Jagat Singh Kirar , Savita Khare\",\"doi\":\"10.1016/j.jics.2024.101395\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Chitosan (Cs) supported heterogeneous catalysts of Fe(III) and Ni(II) is developed by the equimolar reaction of two schiff base ligands, L<sub>1</sub> [Cs-HACP] and L<sub>2</sub> [ANI-HACP] and Metal salts {where Metal = Fe(III) and Ni(II)}with chitosan. The L<sub>1</sub> ligand is prepared by the reaction of chitosan (Cs) and ortho hydroxyl (HACP) acetophenone in methanol and L<sub>2</sub> ligand is prepared by the condensation of aniline (ANI) and ortho hydroxyl acetophenone (HACP) in solvent free condition. The prepared catalysts {M-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>} are characterized by different analytical techniques viz. scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), powder X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), Raman, UV-VIS-NIR, X-ray photoelectron spectroscopy (XPS) and computational studies. The catalytic behavior of newly synthesized catalysts are tested for the C–H activation using 70 % <em>tert</em>-butyl hydroperoxide (TBHP). The best results are obtained for tetralin oxidation. The order of catalytic reactivity of {M-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>}catalyst is in decreasing order: {Fe(III)-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>} > {Ni(II)-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>}. The {Fe(III)-[Cs-L<sub>1</sub>-L<sub>2</sub>]Cl<sub>2</sub>} gives maximum conversion 81.99 % of tetralin with 84.50 % selectivity of tetralone (T-lone) and 6.47 % selectivity of tetralol (T-lol) after 5 h of reaction at 80 °C temperature. The chitosan based heterogeneous catalyst is easy to separate and recover. It can be recycled seven times.</div></div>\",\"PeriodicalId\":17276,\"journal\":{\"name\":\"Journal of the Indian Chemical Society\",\"volume\":\"101 11\",\"pages\":\"Article 101395\"},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2024-09-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the Indian Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0019452224002759\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the Indian Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0019452224002759","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
C–H bond activation over chitosan based Fe(III) and Ni(II) catalysts
Chitosan (Cs) supported heterogeneous catalysts of Fe(III) and Ni(II) is developed by the equimolar reaction of two schiff base ligands, L1 [Cs-HACP] and L2 [ANI-HACP] and Metal salts {where Metal = Fe(III) and Ni(II)}with chitosan. The L1 ligand is prepared by the reaction of chitosan (Cs) and ortho hydroxyl (HACP) acetophenone in methanol and L2 ligand is prepared by the condensation of aniline (ANI) and ortho hydroxyl acetophenone (HACP) in solvent free condition. The prepared catalysts {M-[Cs-L1-L2]Cl2} are characterized by different analytical techniques viz. scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), powder X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), Raman, UV-VIS-NIR, X-ray photoelectron spectroscopy (XPS) and computational studies. The catalytic behavior of newly synthesized catalysts are tested for the C–H activation using 70 % tert-butyl hydroperoxide (TBHP). The best results are obtained for tetralin oxidation. The order of catalytic reactivity of {M-[Cs-L1-L2]Cl2}catalyst is in decreasing order: {Fe(III)-[Cs-L1-L2]Cl2} > {Ni(II)-[Cs-L1-L2]Cl2}. The {Fe(III)-[Cs-L1-L2]Cl2} gives maximum conversion 81.99 % of tetralin with 84.50 % selectivity of tetralone (T-lone) and 6.47 % selectivity of tetralol (T-lol) after 5 h of reaction at 80 °C temperature. The chitosan based heterogeneous catalyst is easy to separate and recover. It can be recycled seven times.
期刊介绍:
The Journal of the Indian Chemical Society publishes original, fundamental, theorical, experimental research work of highest quality in all areas of chemistry, biochemistry, medicinal chemistry, electrochemistry, agrochemistry, chemical engineering and technology, food chemistry, environmental chemistry, etc.