Claudia N. Robison, , , Madalyn Phan, , , Leroy E. Laverman, , and , Peter C. Ford*,
{"title":"过氧化氢在碱性溶液中介导羰基锰的氧化。","authors":"Claudia N. Robison, , , Madalyn Phan, , , Leroy E. Laverman, , and , Peter C. Ford*, ","doi":"10.1021/acs.inorgchem.5c02269","DOIUrl":null,"url":null,"abstract":"<p >Reported are stopped-flow kinetics studies of the hydrogen peroxide reaction with the water-soluble manganese(I) carbonyl complex. <i>fac</i>-[Mn(CO)<sub>3</sub>(Br)(bpCO<sub>2</sub>)]<sup>2–</sup> (<b>I</b>, bpCO<sub>2</sub><sup>2–</sup> = 2,2′-bipyridine-4,4′-dicarboxylate dianion) in alkaline solution. In an earlier study, the H<sub>2</sub>O<sub>2</sub> oxidation of <b>I</b> was shown to be accompanied by the release of more than two equivalents of carbon monoxide. The stopped-flow studies here confirm the strongly pH dependence of the reaction rate, and a revised mechanism for this kinetics behavior is proposed. The larger interest in these systems derives from evaluating redox mechanisms for CO delivery from metal-based carbon monoxide releasing moieties (CORMs) under physiologically relevant conditions.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 40","pages":"19973–19979"},"PeriodicalIF":4.7000,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Hydrogen Peroxide Mediated Oxidation of Manganese Carbonyls in Alkaline Solution\",\"authors\":\"Claudia N. Robison, , , Madalyn Phan, , , Leroy E. Laverman, , and , Peter C. Ford*, \",\"doi\":\"10.1021/acs.inorgchem.5c02269\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Reported are stopped-flow kinetics studies of the hydrogen peroxide reaction with the water-soluble manganese(I) carbonyl complex. <i>fac</i>-[Mn(CO)<sub>3</sub>(Br)(bpCO<sub>2</sub>)]<sup>2–</sup> (<b>I</b>, bpCO<sub>2</sub><sup>2–</sup> = 2,2′-bipyridine-4,4′-dicarboxylate dianion) in alkaline solution. In an earlier study, the H<sub>2</sub>O<sub>2</sub> oxidation of <b>I</b> was shown to be accompanied by the release of more than two equivalents of carbon monoxide. The stopped-flow studies here confirm the strongly pH dependence of the reaction rate, and a revised mechanism for this kinetics behavior is proposed. The larger interest in these systems derives from evaluating redox mechanisms for CO delivery from metal-based carbon monoxide releasing moieties (CORMs) under physiologically relevant conditions.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 40\",\"pages\":\"19973–19979\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-08-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02269\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02269","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Hydrogen Peroxide Mediated Oxidation of Manganese Carbonyls in Alkaline Solution
Reported are stopped-flow kinetics studies of the hydrogen peroxide reaction with the water-soluble manganese(I) carbonyl complex. fac-[Mn(CO)3(Br)(bpCO2)]2– (I, bpCO22– = 2,2′-bipyridine-4,4′-dicarboxylate dianion) in alkaline solution. In an earlier study, the H2O2 oxidation of I was shown to be accompanied by the release of more than two equivalents of carbon monoxide. The stopped-flow studies here confirm the strongly pH dependence of the reaction rate, and a revised mechanism for this kinetics behavior is proposed. The larger interest in these systems derives from evaluating redox mechanisms for CO delivery from metal-based carbon monoxide releasing moieties (CORMs) under physiologically relevant conditions.
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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