Wowa Stroek, Nathalie A. V. Rowlinson, Martin Keilwerth, Daniel M. Pividori, Karsten Meyer and Martin Albrecht*,
{"title":"Using PMHS for Catalytic Hydrosilylation with Dimeric Iron Complexes Featuring Mesoionic Carbene Ligands","authors":"Wowa Stroek, Nathalie A. V. Rowlinson, Martin Keilwerth, Daniel M. Pividori, Karsten Meyer and Martin Albrecht*, ","doi":"10.1021/acs.organomet.4c00180","DOIUrl":null,"url":null,"abstract":"<p >While the reduction of unsaturated bonds is well established by catalytic hydrogenation reactions using H<sub>2</sub>, alternative approaches are appealing for environmental and safety reasons. One of these methods is the catalytic hydrosilylation reaction, which becomes environmentally very friendly when using polymethylhydrosiloxane (PMHS), a waste product from the silicon industry, as a hydrosilylation agent. Here, we report the synthesis and catalytic activity of a range of iron triazolylidene complexes for the hydrosilylation of carbonyls using PMHS with unprecedented turnover numbers up to 72,000. Various functional groups on the substrate aromatic ring are tolerated, including CN, Br, OMe, and NMe<sub>2</sub> substituents. The hydrosilylation is not restricted to benzylic ketones and aldehydes, esters, and amides are also converted. Rather remarkable for hydrosilylation, ketones are converted faster than aldehydes. Intermolecular competition experiments suggest that the active catalyst is formed by the coordination of a ketone, which rationalizes the origin of this untypical substrate reactivity trend.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-06-11","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.4c00180","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
Abstract
While the reduction of unsaturated bonds is well established by catalytic hydrogenation reactions using H2, alternative approaches are appealing for environmental and safety reasons. One of these methods is the catalytic hydrosilylation reaction, which becomes environmentally very friendly when using polymethylhydrosiloxane (PMHS), a waste product from the silicon industry, as a hydrosilylation agent. Here, we report the synthesis and catalytic activity of a range of iron triazolylidene complexes for the hydrosilylation of carbonyls using PMHS with unprecedented turnover numbers up to 72,000. Various functional groups on the substrate aromatic ring are tolerated, including CN, Br, OMe, and NMe2 substituents. The hydrosilylation is not restricted to benzylic ketones and aldehydes, esters, and amides are also converted. Rather remarkable for hydrosilylation, ketones are converted faster than aldehydes. Intermolecular competition experiments suggest that the active catalyst is formed by the coordination of a ketone, which rationalizes the origin of this untypical substrate reactivity trend.
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.