{"title":"利用[MnIV2(μ-O)3(tmtacn)2]2+ 和过氧化氢在水中将 HMF 良性、选择性催化氧化为 HMFCA 的见解","authors":"Jan Oene Paul Broekman, and , Peter J. Deuss*, ","doi":"10.1021/acs.organomet.4c00109","DOIUrl":null,"url":null,"abstract":"<p >5-Hydroxymethylfurfural (HMF) is a biobased platform chemical with a lot of potential to be a key chemical in a future chemical industry. Oxidized derivatives of HMF are explored in many emerging chemical products. However, selective oxidation toward 5-hydroxymethyl-2-furan carboxylic acid (HMFCA) is challenging. Furthermore, this conversion has been hardly explored with homogeneous catalysts. We show here the selective oxidation toward HMFCA using the industrially relevant catalyst [Mn<sup>IV</sup><sub>2</sub>(μ-O)<sub>3</sub>(tmtacn)<sub>2</sub>][(X)<sub>2</sub>] (<b>Mncat</b>, X = CH<sub>3</sub>COO/PF<sub>6</sub>/SO<sub>4</sub>). Moreover, this is achieved in water, under mild conditions (room temperature, pH 11), using low loadings of a nonprecious metal catalyst and hydrogen peroxide, reaching TONs of up to 200 mol<sub>HMFCA</sub>/mol<sub><b>Mncat</b></sub>. We show that the oxidation under these conditions behaves distinctively from the oxidation with <b>Mncat</b> in MeCN and allows selective oxidation of aldehydes in the presence of alcohols. Kinetic and ESI-MS studies were used to study the change in selectivity and to give an explanation for changes in catalytic behavior.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00109","citationCount":"0","resultStr":"{\"title\":\"Insights into the Benign, Selective Catalytic Oxidation of HMF to HMFCA in Water Using [MnIV2(μ-O)3(tmtacn)2]2+ and Hydrogen Peroxide\",\"authors\":\"Jan Oene Paul Broekman, and , Peter J. Deuss*, \",\"doi\":\"10.1021/acs.organomet.4c00109\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >5-Hydroxymethylfurfural (HMF) is a biobased platform chemical with a lot of potential to be a key chemical in a future chemical industry. Oxidized derivatives of HMF are explored in many emerging chemical products. However, selective oxidation toward 5-hydroxymethyl-2-furan carboxylic acid (HMFCA) is challenging. Furthermore, this conversion has been hardly explored with homogeneous catalysts. We show here the selective oxidation toward HMFCA using the industrially relevant catalyst [Mn<sup>IV</sup><sub>2</sub>(μ-O)<sub>3</sub>(tmtacn)<sub>2</sub>][(X)<sub>2</sub>] (<b>Mncat</b>, X = CH<sub>3</sub>COO/PF<sub>6</sub>/SO<sub>4</sub>). Moreover, this is achieved in water, under mild conditions (room temperature, pH 11), using low loadings of a nonprecious metal catalyst and hydrogen peroxide, reaching TONs of up to 200 mol<sub>HMFCA</sub>/mol<sub><b>Mncat</b></sub>. We show that the oxidation under these conditions behaves distinctively from the oxidation with <b>Mncat</b> in MeCN and allows selective oxidation of aldehydes in the presence of alcohols. Kinetic and ESI-MS studies were used to study the change in selectivity and to give an explanation for changes in catalytic behavior.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-05-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00109\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00109\",\"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":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00109","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Insights into the Benign, Selective Catalytic Oxidation of HMF to HMFCA in Water Using [MnIV2(μ-O)3(tmtacn)2]2+ and Hydrogen Peroxide
5-Hydroxymethylfurfural (HMF) is a biobased platform chemical with a lot of potential to be a key chemical in a future chemical industry. Oxidized derivatives of HMF are explored in many emerging chemical products. However, selective oxidation toward 5-hydroxymethyl-2-furan carboxylic acid (HMFCA) is challenging. Furthermore, this conversion has been hardly explored with homogeneous catalysts. We show here the selective oxidation toward HMFCA using the industrially relevant catalyst [MnIV2(μ-O)3(tmtacn)2][(X)2] (Mncat, X = CH3COO/PF6/SO4). Moreover, this is achieved in water, under mild conditions (room temperature, pH 11), using low loadings of a nonprecious metal catalyst and hydrogen peroxide, reaching TONs of up to 200 molHMFCA/molMncat. We show that the oxidation under these conditions behaves distinctively from the oxidation with Mncat in MeCN and allows selective oxidation of aldehydes in the presence of alcohols. Kinetic and ESI-MS studies were used to study the change in selectivity and to give an explanation for changes in catalytic behavior.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.