{"title":"Heme and nonheme high-valent manganese(V)-oxo complexes: Synthesis, characterization, and reactivity","authors":"Chunxia Wu, Jie Chen, Wonwoo Nam, Bin Wang","doi":"10.1016/j.ccr.2024.216429","DOIUrl":null,"url":null,"abstract":"High-valent metal-oxo species have been proposed, and in certain instances confirmed, as the key intermediates in enzymatic and biomimetic oxidation reactions. Further, high-valent Mn-oxo species are considered as the active intermediates responsible for water oxidation in Photosystem II and catalytic water oxidation reactions by synthetic metal catalysts. Identification of these intermediates is crucial for understanding the fundamental principles of enzymatic and biomimetic reactions. However, the active intermediates in oxidation reactions, especially the high-valent metal-oxo species, have short lifetimes and are highly reactive in nature, causing significant challenges for capturing and characterizing in mechanistic studies. Therefore, synthetic high-valent metal-oxo complexes have garnered significant interest among chemists. In this review, we provide a systematic overview of the synthesis and structural and spectroscopic characterization of both heme and nonheme Mn<sup>V</sup>-oxo complexes, along with their reactivities in hydrogen-atom transfer (HAT), oxygen-atom transfer (OAT), electron-transfer (ET), and O−O bond formation reactions. Emphasis is also placed on the influence of the ligands, the presence of axial ligands, the kinds of solvents, and the use of Lewis or Brønsted acids on the electronic structures, chemical properties, reactivities, and reaction mechanisms of the heme and nonheme Mn<sup>V</sup>-oxo complexes.","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"6 1","pages":""},"PeriodicalIF":20.3000,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Coordination Chemistry Reviews","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/j.ccr.2024.216429","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
High-valent metal-oxo species have been proposed, and in certain instances confirmed, as the key intermediates in enzymatic and biomimetic oxidation reactions. Further, high-valent Mn-oxo species are considered as the active intermediates responsible for water oxidation in Photosystem II and catalytic water oxidation reactions by synthetic metal catalysts. Identification of these intermediates is crucial for understanding the fundamental principles of enzymatic and biomimetic reactions. However, the active intermediates in oxidation reactions, especially the high-valent metal-oxo species, have short lifetimes and are highly reactive in nature, causing significant challenges for capturing and characterizing in mechanistic studies. Therefore, synthetic high-valent metal-oxo complexes have garnered significant interest among chemists. In this review, we provide a systematic overview of the synthesis and structural and spectroscopic characterization of both heme and nonheme MnV-oxo complexes, along with their reactivities in hydrogen-atom transfer (HAT), oxygen-atom transfer (OAT), electron-transfer (ET), and O−O bond formation reactions. Emphasis is also placed on the influence of the ligands, the presence of axial ligands, the kinds of solvents, and the use of Lewis or Brønsted acids on the electronic structures, chemical properties, reactivities, and reaction mechanisms of the heme and nonheme MnV-oxo complexes.
期刊介绍:
Coordination Chemistry Reviews offers rapid publication of review articles on current and significant topics in coordination chemistry, encompassing organometallic, supramolecular, theoretical, and bioinorganic chemistry. It also covers catalysis, materials chemistry, and metal-organic frameworks from a coordination chemistry perspective. Reviews summarize recent developments or discuss specific techniques, welcoming contributions from both established and emerging researchers.
The journal releases special issues on timely subjects, including those featuring contributions from specific regions or conferences. Occasional full-length book articles are also featured. Additionally, special volumes cover annual reviews of main group chemistry, transition metal group chemistry, and organometallic chemistry. These comprehensive reviews are vital resources for those engaged in coordination chemistry, further establishing Coordination Chemistry Reviews as a hub for insightful surveys in inorganic and physical inorganic chemistry.