{"title":"分子氧与水溶液中[CoII(1,4,8,11-四氮杂环十四烷)]的结合特征","authors":"Lu Quan Hau, Laouénan André, L’Her Maurice","doi":"10.1016/j.ica.2024.122437","DOIUrl":null,"url":null,"abstract":"<div><div>1, 4, 8,11-tetraazacyclotetradecane (cyclam), a cyclic tetramine, binds various metal cations among which Co<sup>2+</sup> is of a particular importance as its complex can bind molecular oxygen and help separate it from nitrogen of air. The stability constants of the O<sub>2</sub> complexes have been the subject of many works but, due to kinetic complications, none of these studies yielded satisfactory results. In the present work spectrophotometry has been used to investigate the acid-base properties of the various species as well as the kinetic and thermodynamic aspects of their formation. For kinetic reasons the superoxo complex is formed primarily which then evolves to the µ-peroxo derivative, the most stable species. This study reveals why the many previous experiments conducted to measure the stability constants of the oxygen complexes have failed.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122437"},"PeriodicalIF":2.7000,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Characterization of molecular oxygen binding to [CoII(1,4,8,11-tetraazacyclotetradecane)] in aqueous solutions\",\"authors\":\"Lu Quan Hau, Laouénan André, L’Her Maurice\",\"doi\":\"10.1016/j.ica.2024.122437\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>1, 4, 8,11-tetraazacyclotetradecane (cyclam), a cyclic tetramine, binds various metal cations among which Co<sup>2+</sup> is of a particular importance as its complex can bind molecular oxygen and help separate it from nitrogen of air. The stability constants of the O<sub>2</sub> complexes have been the subject of many works but, due to kinetic complications, none of these studies yielded satisfactory results. In the present work spectrophotometry has been used to investigate the acid-base properties of the various species as well as the kinetic and thermodynamic aspects of their formation. For kinetic reasons the superoxo complex is formed primarily which then evolves to the µ-peroxo derivative, the most stable species. This study reveals why the many previous experiments conducted to measure the stability constants of the oxygen complexes have failed.</div></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":\"575 \",\"pages\":\"Article 122437\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-11-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0020169324005280\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324005280","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Characterization of molecular oxygen binding to [CoII(1,4,8,11-tetraazacyclotetradecane)] in aqueous solutions
1, 4, 8,11-tetraazacyclotetradecane (cyclam), a cyclic tetramine, binds various metal cations among which Co2+ is of a particular importance as its complex can bind molecular oxygen and help separate it from nitrogen of air. The stability constants of the O2 complexes have been the subject of many works but, due to kinetic complications, none of these studies yielded satisfactory results. In the present work spectrophotometry has been used to investigate the acid-base properties of the various species as well as the kinetic and thermodynamic aspects of their formation. For kinetic reasons the superoxo complex is formed primarily which then evolves to the µ-peroxo derivative, the most stable species. This study reveals why the many previous experiments conducted to measure the stability constants of the oxygen complexes have failed.
期刊介绍：
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.
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