Limashree Sahoo, Payal Panwar, Chivukula V. Sastri, Sam P. de Visser
{"title":"揭示赤道异构体取代的非血红素铁络合物中的亚氯酸盐氧化途径","authors":"Limashree Sahoo, Payal Panwar, Chivukula V. Sastri, Sam P. de Visser","doi":"10.1021/acsorginorgau.4c00045","DOIUrl":null,"url":null,"abstract":"The first-coordination sphere of catalysts is known to play a crucial role in reaction mechanisms, but details of how equatorial ligands influence the reactivity remain unknown. Heteroatom ligated to the equatorial position of iron centers in nonheme iron metalloenzymes modulates structure and reactivity. To investigate the impact of equatorial heteroatom substitution on chlorite oxidation, we synthesized and characterized three novel mononuclear nonheme iron(II) complexes with a pentadentate bispidine scaffold. These complexes feature systematic substitutions at the equatorial position in the bispidine ligand framework where the pyridine group is replaced with NMe<sub>2</sub>, SMe, and OMe groups. The three iron(II)–bispidine complexes were subjected to studies in chlorite oxidation reactions as a model pathway for oxygen atom transfer. Chlorine oxyanions, which have the halide in an oxidation state ranging from +1 to +7, have numerous applications but can contaminate water bodies, and this demands urgent environmental remediation. Chlorite, a common precursor to chlorine dioxide, is of particular interest due to the superior antimicrobial activity of chlorine dioxide. Moreover, its generation leads to fewer harmful byproducts in water treatment. Here, we demonstrate that these complexes can produce chlorine dioxide from chlorite in acetate buffer at room temperature and pH 5.0, oxidizing chlorite through the in situ formation of high-valent iron(IV)–oxo intermediates. This study establishes how subtle changes in the coordination sphere around iron can influence the reactivity.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes\",\"authors\":\"Limashree Sahoo, Payal Panwar, Chivukula V. Sastri, Sam P. de Visser\",\"doi\":\"10.1021/acsorginorgau.4c00045\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The first-coordination sphere of catalysts is known to play a crucial role in reaction mechanisms, but details of how equatorial ligands influence the reactivity remain unknown. Heteroatom ligated to the equatorial position of iron centers in nonheme iron metalloenzymes modulates structure and reactivity. To investigate the impact of equatorial heteroatom substitution on chlorite oxidation, we synthesized and characterized three novel mononuclear nonheme iron(II) complexes with a pentadentate bispidine scaffold. These complexes feature systematic substitutions at the equatorial position in the bispidine ligand framework where the pyridine group is replaced with NMe<sub>2</sub>, SMe, and OMe groups. The three iron(II)–bispidine complexes were subjected to studies in chlorite oxidation reactions as a model pathway for oxygen atom transfer. Chlorine oxyanions, which have the halide in an oxidation state ranging from +1 to +7, have numerous applications but can contaminate water bodies, and this demands urgent environmental remediation. Chlorite, a common precursor to chlorine dioxide, is of particular interest due to the superior antimicrobial activity of chlorine dioxide. Moreover, its generation leads to fewer harmful byproducts in water treatment. Here, we demonstrate that these complexes can produce chlorine dioxide from chlorite in acetate buffer at room temperature and pH 5.0, oxidizing chlorite through the in situ formation of high-valent iron(IV)–oxo intermediates. This study establishes how subtle changes in the coordination sphere around iron can influence the reactivity.\",\"PeriodicalId\":29797,\"journal\":{\"name\":\"ACS Organic & Inorganic Au\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2024-09-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Organic & Inorganic Au\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1021/acsorginorgau.4c00045\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Organic & Inorganic Au","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1021/acsorginorgau.4c00045","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Unraveling Chlorite Oxidation Pathways in Equatorially Heteroatom-Substituted Nonheme Iron Complexes
The first-coordination sphere of catalysts is known to play a crucial role in reaction mechanisms, but details of how equatorial ligands influence the reactivity remain unknown. Heteroatom ligated to the equatorial position of iron centers in nonheme iron metalloenzymes modulates structure and reactivity. To investigate the impact of equatorial heteroatom substitution on chlorite oxidation, we synthesized and characterized three novel mononuclear nonheme iron(II) complexes with a pentadentate bispidine scaffold. These complexes feature systematic substitutions at the equatorial position in the bispidine ligand framework where the pyridine group is replaced with NMe2, SMe, and OMe groups. The three iron(II)–bispidine complexes were subjected to studies in chlorite oxidation reactions as a model pathway for oxygen atom transfer. Chlorine oxyanions, which have the halide in an oxidation state ranging from +1 to +7, have numerous applications but can contaminate water bodies, and this demands urgent environmental remediation. Chlorite, a common precursor to chlorine dioxide, is of particular interest due to the superior antimicrobial activity of chlorine dioxide. Moreover, its generation leads to fewer harmful byproducts in water treatment. Here, we demonstrate that these complexes can produce chlorine dioxide from chlorite in acetate buffer at room temperature and pH 5.0, oxidizing chlorite through the in situ formation of high-valent iron(IV)–oxo intermediates. This study establishes how subtle changes in the coordination sphere around iron can influence the reactivity.
期刊介绍:
ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.