Ilya K. Mikhailov, Zufar N. Gafurov, Alexey A. Kagilev, Il’yas F. Sakhapov, Vladimir I. Morozov, Gumar R. Ganeev, Khasan R. Khayarov, Vasilisa A. Kulikova, Vladislava A. Kirkina, Evgenii I. Gutsul, Elena S. Shubina, Natalia V. Belkova, Oleg G. Sinyashin, Dmitry G. Yakhvarov
{"title":"含有非无害二酰胺基/双(膦)钳配体的镍、钯和铂配合物对 2-氨基乙醇的电催化自由基降解作用","authors":"Ilya K. Mikhailov, Zufar N. Gafurov, Alexey A. Kagilev, Il’yas F. Sakhapov, Vladimir I. Morozov, Gumar R. Ganeev, Khasan R. Khayarov, Vasilisa A. Kulikova, Vladislava A. Kirkina, Evgenii I. Gutsul, Elena S. Shubina, Natalia V. Belkova, Oleg G. Sinyashin, Dmitry G. Yakhvarov","doi":"10.1007/s00723-024-01710-7","DOIUrl":null,"url":null,"abstract":"<div><p>The electrocatalytic activity of PNP pincer complexes with general formula (PNP)MCl (PNP is bis(2-diisopropylphosphino-4-methylphenyl)amide; M = nickel, palladium and platinum) in the oxidative 2-aminoethanol (MEA, a recalcitrant pollutant) degradation process was studied using cyclic voltammetry method. Complexes fulfil the requirements typically expected of a redox mediator or catalyst. Their electrochemical oxidation yields the aminyl radical species which unpaired electron is localized on the ligand. The mechanism of interaction of these aminyl radical complexes with MEA was studied using ESR- and NMR-spectroscopy methods. The addition of MEA to the solution of model platinum derivative leads to the disappearance of the ESR signal responsible for the aminyl radical complex, whereas the <sup>31</sup>P{<sup>1</sup>H} NMR spectrum revealed the regeneration of neutral (PNP)MCl. Palladium derivative was found to be the most effective catalyst of the series with an I<sub>cat</sub>/I<sub>p</sub> value of 6.7. Controlled potential electrolysis has allowed us to identify the main products of the catalytic process and to propose the mechanism of the overall process.</p></div>","PeriodicalId":469,"journal":{"name":"Applied Magnetic Resonance","volume":"55 10","pages":"1323 - 1333"},"PeriodicalIF":1.1000,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Electrocatalytic Radical Degradation of 2-Aminoethanol by Nickel, Palladium and Platinum Complexes Bearing Non-Innocent Diarylamido/bis(Phosphine) Pincer Ligand\",\"authors\":\"Ilya K. Mikhailov, Zufar N. Gafurov, Alexey A. Kagilev, Il’yas F. Sakhapov, Vladimir I. Morozov, Gumar R. Ganeev, Khasan R. Khayarov, Vasilisa A. Kulikova, Vladislava A. Kirkina, Evgenii I. Gutsul, Elena S. Shubina, Natalia V. Belkova, Oleg G. Sinyashin, Dmitry G. Yakhvarov\",\"doi\":\"10.1007/s00723-024-01710-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The electrocatalytic activity of PNP pincer complexes with general formula (PNP)MCl (PNP is bis(2-diisopropylphosphino-4-methylphenyl)amide; M = nickel, palladium and platinum) in the oxidative 2-aminoethanol (MEA, a recalcitrant pollutant) degradation process was studied using cyclic voltammetry method. Complexes fulfil the requirements typically expected of a redox mediator or catalyst. Their electrochemical oxidation yields the aminyl radical species which unpaired electron is localized on the ligand. The mechanism of interaction of these aminyl radical complexes with MEA was studied using ESR- and NMR-spectroscopy methods. The addition of MEA to the solution of model platinum derivative leads to the disappearance of the ESR signal responsible for the aminyl radical complex, whereas the <sup>31</sup>P{<sup>1</sup>H} NMR spectrum revealed the regeneration of neutral (PNP)MCl. Palladium derivative was found to be the most effective catalyst of the series with an I<sub>cat</sub>/I<sub>p</sub> value of 6.7. Controlled potential electrolysis has allowed us to identify the main products of the catalytic process and to propose the mechanism of the overall process.</p></div>\",\"PeriodicalId\":469,\"journal\":{\"name\":\"Applied Magnetic Resonance\",\"volume\":\"55 10\",\"pages\":\"1323 - 1333\"},\"PeriodicalIF\":1.1000,\"publicationDate\":\"2024-09-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Magnetic Resonance\",\"FirstCategoryId\":\"101\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s00723-024-01710-7\",\"RegionNum\":4,\"RegionCategory\":\"物理与天体物理\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Magnetic Resonance","FirstCategoryId":"101","ListUrlMain":"https://link.springer.com/article/10.1007/s00723-024-01710-7","RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL","Score":null,"Total":0}
Electrocatalytic Radical Degradation of 2-Aminoethanol by Nickel, Palladium and Platinum Complexes Bearing Non-Innocent Diarylamido/bis(Phosphine) Pincer Ligand
The electrocatalytic activity of PNP pincer complexes with general formula (PNP)MCl (PNP is bis(2-diisopropylphosphino-4-methylphenyl)amide; M = nickel, palladium and platinum) in the oxidative 2-aminoethanol (MEA, a recalcitrant pollutant) degradation process was studied using cyclic voltammetry method. Complexes fulfil the requirements typically expected of a redox mediator or catalyst. Their electrochemical oxidation yields the aminyl radical species which unpaired electron is localized on the ligand. The mechanism of interaction of these aminyl radical complexes with MEA was studied using ESR- and NMR-spectroscopy methods. The addition of MEA to the solution of model platinum derivative leads to the disappearance of the ESR signal responsible for the aminyl radical complex, whereas the 31P{1H} NMR spectrum revealed the regeneration of neutral (PNP)MCl. Palladium derivative was found to be the most effective catalyst of the series with an Icat/Ip value of 6.7. Controlled potential electrolysis has allowed us to identify the main products of the catalytic process and to propose the mechanism of the overall process.
期刊介绍:
Applied Magnetic Resonance provides an international forum for the application of magnetic resonance in physics, chemistry, biology, medicine, geochemistry, ecology, engineering, and related fields.
The contents include articles with a strong emphasis on new applications, and on new experimental methods. Additional features include book reviews and Letters to the Editor.