{"title":"Probing the generation, reactivity, and kinetics of high-valent manganese-oxo phthalocyanines: Insights into oxidation mechanisms","authors":"Alexis Smith, Sobenna Onyeso, Tristan Skipworth, Candice Schlabach, Rui Zhang","doi":"10.1016/j.jinorgbio.2025.112872","DOIUrl":null,"url":null,"abstract":"<div><div>In this study, manganese(IV)-oxo phthalocyanines [Mn<sup>IV</sup>(Pc)(O)] (<strong>3</strong>) (Pc = phthalocyanine) were produced either through visible light photolysis of [Mn<sup>III</sup>(Pc)(ClO<sub>3</sub>)] or by chemical oxidation of [Mn<sup>III</sup>(Pc)Cl] (<strong>1</strong>) with iodobenzene diacetate. The manganese(IV)-oxo species under study include tetra-<em>tert</em>-butylphthalocyaine‑manganese(IV)-oxo (<strong>3a</strong>) and phthalocyanine‑manganese(IV)-oxo (<strong>3b</strong>). As anticipated, the generated <strong>3</strong> reacted with various organic substrates to yield the oxidized products and further proved to be a competent oxidant via an H<sub>2</sub><sup>18</sup>O isotope labeling experiment. The kinetics of oxygen atom transfer (OAT) reactions for these generated <strong>3</strong> species with a range of substrates were examined in CH<sub>3</sub>CN solutions unless other specified. Overall, the second-order rate constants under pseudo-first-order conditions for <strong>3a</strong> and <strong>3b</strong> with the same substrates display similar modest reactivity, with the nature of the substrate playing a major role in influencing the reactivity of species <strong>3</strong>. The phenol substrates, in particular, reacted the fastest. Of note, second-order rate constants determined for thioanisoles are comparable to those of alkene epoxidations and activated C<img>H bond oxidations. Conventional Hammett analyses of rate constants for substituted styrenes revealed a linear correlation with the σ constant, indicating minimal charge developed at the transition state during the oxidation process. Additionally, the competition product studies and the Hammett correlation analysis further suggested that the manganese(IV)-oxo species observed in those kinetic studies are unlikely to serve as the primary oxidant for the epoxidation reactions catalyzed by manganese(III) phthalocyanine with PhI(OAc)<sub>2</sub>.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"267 ","pages":"Article 112872"},"PeriodicalIF":3.8000,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Inorganic Biochemistry","FirstCategoryId":"99","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0162013425000522","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}
引用次数: 0
Abstract
In this study, manganese(IV)-oxo phthalocyanines [MnIV(Pc)(O)] (3) (Pc = phthalocyanine) were produced either through visible light photolysis of [MnIII(Pc)(ClO3)] or by chemical oxidation of [MnIII(Pc)Cl] (1) with iodobenzene diacetate. The manganese(IV)-oxo species under study include tetra-tert-butylphthalocyaine‑manganese(IV)-oxo (3a) and phthalocyanine‑manganese(IV)-oxo (3b). As anticipated, the generated 3 reacted with various organic substrates to yield the oxidized products and further proved to be a competent oxidant via an H218O isotope labeling experiment. The kinetics of oxygen atom transfer (OAT) reactions for these generated 3 species with a range of substrates were examined in CH3CN solutions unless other specified. Overall, the second-order rate constants under pseudo-first-order conditions for 3a and 3b with the same substrates display similar modest reactivity, with the nature of the substrate playing a major role in influencing the reactivity of species 3. The phenol substrates, in particular, reacted the fastest. Of note, second-order rate constants determined for thioanisoles are comparable to those of alkene epoxidations and activated CH bond oxidations. Conventional Hammett analyses of rate constants for substituted styrenes revealed a linear correlation with the σ constant, indicating minimal charge developed at the transition state during the oxidation process. Additionally, the competition product studies and the Hammett correlation analysis further suggested that the manganese(IV)-oxo species observed in those kinetic studies are unlikely to serve as the primary oxidant for the epoxidation reactions catalyzed by manganese(III) phthalocyanine with PhI(OAc)2.
期刊介绍:
The Journal of Inorganic Biochemistry is an established international forum for research in all aspects of Biological Inorganic Chemistry. Original papers of a high scientific level are published in the form of Articles (full length papers), Short Communications, Focused Reviews and Bioinorganic Methods. Topics include: the chemistry, structure and function of metalloenzymes; the interaction of inorganic ions and molecules with proteins and nucleic acids; the synthesis and properties of coordination complexes of biological interest including both structural and functional model systems; the function of metal- containing systems in the regulation of gene expression; the role of metals in medicine; the application of spectroscopic methods to determine the structure of metallobiomolecules; the preparation and characterization of metal-based biomaterials; and related systems. The emphasis of the Journal is on the structure and mechanism of action of metallobiomolecules.