{"title":"Second sphere control of CO2 reduction selectivity by iron porphyrins: The role of spin state","authors":"Suman Patra , Soumili Ghosh , Soumya Samanta, Abhijit Nayek, Abhishek Dey","doi":"10.1016/j.jorganchem.2024.123439","DOIUrl":null,"url":null,"abstract":"<div><div>Iron porphyrins are reported to reduce CO<sub>2</sub> selectively to CO. Hydrogen bonding interactions are reported to facilitate this 2e<sup>−</sup>/2H<sup>+</sup> reduction process. A series of iron porphyrins are reported here where hydrogen bonding distal super structure is introduced systematically. The results show that the selectivity for 2e<sup>−</sup>/2H<sup>+</sup> CO<sub>2</sub> reduction changes dramatically from CO to HCOOH as hydrogen bonding interactions are introduced. The resonance Raman data of the Fe(II)-COOH intermediate, trapped at −80<sup>o</sup>C, show that the spin state of this species changes from low spin to high spin as hydrogen bonding is introduced. The spin state of the Fe(II)-COOH intermediate seems to determine the selectivity of 2e<sup>−</sup>/2H<sup>+</sup> CO<sub>2</sub> reduction in iron porphyrins.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123439"},"PeriodicalIF":2.1000,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X24004340","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Iron porphyrins are reported to reduce CO2 selectively to CO. Hydrogen bonding interactions are reported to facilitate this 2e−/2H+ reduction process. A series of iron porphyrins are reported here where hydrogen bonding distal super structure is introduced systematically. The results show that the selectivity for 2e−/2H+ CO2 reduction changes dramatically from CO to HCOOH as hydrogen bonding interactions are introduced. The resonance Raman data of the Fe(II)-COOH intermediate, trapped at −80oC, show that the spin state of this species changes from low spin to high spin as hydrogen bonding is introduced. The spin state of the Fe(II)-COOH intermediate seems to determine the selectivity of 2e−/2H+ CO2 reduction in iron porphyrins.
据报道，铁卟啉可选择性地将 CO2 还原成 CO。据报道，氢键相互作用促进了这种 2e-/2H+ 还原过程。本文报告了一系列铁卟啉，其中系统地引入了氢键远端超级结构。结果表明，随着氢键相互作用的引入，2e-/2H+ CO2 还原的选择性从 CO 显著变为 HCOOH。在 -80oC 下捕获的 Fe(II)-COOH 中间体的共振拉曼数据显示，随着氢键的引入，该物种的自旋态从低自旋变为高自旋。Fe(II)-COOH 中间体的自旋状态似乎决定了铁卟啉中 2e-/2H+ CO2 还原的选择性。
期刊介绍：
The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds.
Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome.
The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.
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