{"title":"环戊二烯酮铁络合物催化的酮类氢化反应:电荷标签对催化性能的影响","authors":"André Bütikofer, Vera Kesselring and Peter Chen*, ","doi":"10.1021/acs.organomet.3c00489","DOIUrl":null,"url":null,"abstract":"<p >The reason for the discrepancy in reaction rate in hydrogenation reactions using cyclopentadienone iron complexes as catalysts, depending on the absence or presence of a negative charge-tag (sulfonate or phosphonate), was investigated experimentally. Based on NMR and kinetic experiments, the direct binding of the charge-tag to the active site of the catalyst and electric field effects influencing transition state energies could be excluded. Preactivation of the catalysts as the monoacetonitrile dicarbonyl complexes was found to be superior to the in situ activation of the tricarbonyl complex with trimethylamine oxide with an up to 32-fold rate enhancement. CO ligand removal from the tricarbonyl iron complexes with Me<sub>3</sub>NO was found to be disfavored in protic solvents compared to polar, aprotic solvents. Micelle formation was observed for the negatively charge-tagged complexes, with critical micelle concentrations in the range of 1.75–17 mM depending on the alkali metal counterion. The presence of the tertiary amine moiety in the charge-tagged catalyst was found to be responsible for the decrease in reaction rate. The presence of micelles was found to increase the reaction rate compared to noncharged complexes bearing a tertiary amine group.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Cyclopentadienone Iron Complex-Catalyzed Hydrogenation of Ketones: The Influence of the Charge-Tag on Catalytic Performance\",\"authors\":\"André Bütikofer, Vera Kesselring and Peter Chen*, \",\"doi\":\"10.1021/acs.organomet.3c00489\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The reason for the discrepancy in reaction rate in hydrogenation reactions using cyclopentadienone iron complexes as catalysts, depending on the absence or presence of a negative charge-tag (sulfonate or phosphonate), was investigated experimentally. Based on NMR and kinetic experiments, the direct binding of the charge-tag to the active site of the catalyst and electric field effects influencing transition state energies could be excluded. Preactivation of the catalysts as the monoacetonitrile dicarbonyl complexes was found to be superior to the in situ activation of the tricarbonyl complex with trimethylamine oxide with an up to 32-fold rate enhancement. CO ligand removal from the tricarbonyl iron complexes with Me<sub>3</sub>NO was found to be disfavored in protic solvents compared to polar, aprotic solvents. Micelle formation was observed for the negatively charge-tagged complexes, with critical micelle concentrations in the range of 1.75–17 mM depending on the alkali metal counterion. The presence of the tertiary amine moiety in the charge-tagged catalyst was found to be responsible for the decrease in reaction rate. The presence of micelles was found to increase the reaction rate compared to noncharged complexes bearing a tertiary amine group.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-04-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.3c00489\",\"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.3c00489","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
实验研究了使用环戊二烯酮铁络合物作为催化剂的氢化反应中,反应速率因负电荷标记(磺酸盐或膦酸盐)的存在与否而存在差异的原因。根据核磁共振和动力学实验,可以排除电荷标签与催化剂活性位点的直接结合以及影响过渡态能量的电场效应。研究发现,催化剂作为单乙腈二羰基络合物的预活化效果优于三羰基络合物与氧化三甲胺的原位活化效果,其速率可提高 32 倍。与极性烷基溶剂相比,在原生质溶剂中,用 Me3NO 从三羰基铁络合物中去除 CO 配体的效果较差。负电荷标记的络合物可形成胶束,临界胶束浓度在 1.75-17 mM 之间,具体取决于碱金属反离子。研究发现,电荷标记催化剂中叔胺分子的存在是导致反应速率降低的原因。与带有叔胺基团的不带电复合物相比,胶束的存在提高了反应速率。
Cyclopentadienone Iron Complex-Catalyzed Hydrogenation of Ketones: The Influence of the Charge-Tag on Catalytic Performance
The reason for the discrepancy in reaction rate in hydrogenation reactions using cyclopentadienone iron complexes as catalysts, depending on the absence or presence of a negative charge-tag (sulfonate or phosphonate), was investigated experimentally. Based on NMR and kinetic experiments, the direct binding of the charge-tag to the active site of the catalyst and electric field effects influencing transition state energies could be excluded. Preactivation of the catalysts as the monoacetonitrile dicarbonyl complexes was found to be superior to the in situ activation of the tricarbonyl complex with trimethylamine oxide with an up to 32-fold rate enhancement. CO ligand removal from the tricarbonyl iron complexes with Me3NO was found to be disfavored in protic solvents compared to polar, aprotic solvents. Micelle formation was observed for the negatively charge-tagged complexes, with critical micelle concentrations in the range of 1.75–17 mM depending on the alkali metal counterion. The presence of the tertiary amine moiety in the charge-tagged catalyst was found to be responsible for the decrease in reaction rate. The presence of micelles was found to increase the reaction rate compared to noncharged complexes bearing a tertiary amine group.
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.