Rhodium–Iodide Complex on a Catalytically Active SiO2 Surface for One‐Pot Hydrosilylation–CO2 Cycloaddition
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Le résumé fourni par la source
Abstract In this study, a novel Rh–iodide complex was synthesized through a surface reaction between an immobilized Rh cyclooctadiene complex and alkylammonium iodide (N+I−) on SiO2. In the presence of ammonium cations, the SiO2‐supported Rh–iodide complex could be effectively used for the one‐pot synthesis of various silylcarbonate derivatives starting from epoxy olefins, hydrosilanes, and CO2. The maximum turnover numbers (TONs) for the hydrosilylation reaction and the CO2 cycloaddition were 7600 (Rh) and 130 (N+I−), respectively. The catalyst exhibited much higher performance for hydrosilylation than solely the Rh complex on SiO2. The mechanism of the Rh‐catalyzed hydrosilylation reaction and the local structure of Rh, which is affected by the co‐immobilized N+I−, were investigated by using Rh and I K‐edge XAFS and XPS. Analysis of the XAFS profiles indicated the presence of a Rh−I bond. The Rh unit was in its electron‐rich state. Curve‐fitting analysis of the Rh K‐edge EXAFS profiles suggests dissociation of the cycloocta‐1,5‐diene (COD) ligand from the Rh center. Results from spectroscopic and kinetic analyses revealed that the high activity of the catalyst (during hydrosilylation) could be attributed to a decrease in steric hindrance and the electron‐rich state of the Rh. The decrease in the steric hindrance could be attributed to the absence of COD, and the electron‐rich state promoted the oxidative addition of Si−H. To the best of our knowledge, this is the first example of a one‐pot silylcarbonate synthesis as well as a determination of a novel surface Rh–iodide complex and its catalysis.
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Le contrôle bibliographique ouvert
DOI retrouvé dans Crossref DOI retrouvé, mais le titre doit être comparé manuellement.
- Titre Crossref
- Rhodium–Iodide Complex on a Catalytically Active SiO<sub>2</sub> Surface for One‐Pot Hydrosilylation–CO<sub>2</sub> Cycloaddition
- Date Crossref
- 29/12/2021
- Éditeur
- Wiley
- Type
- journal-article
Ce recoupement confirme des métadonnées liées au DOI. Il ne confirme ni la méthode ni les conclusions de l’étude, et il ne compte pas comme une seconde source scientifique indépendante.
Où se fait cette recherche
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Tokyo Institute of Technology Department of Chemical Science and Engineering pays non établi dans la noticeUniversité ou école supérieure
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Yokohama National University Department of Chemistry and Life Science pays non établi dans la noticeUniversité ou école supérieure
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National Institute of Advanced Industrial Science and Technology pays non établi dans la noticeOrganisme public
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International Christian University pays non établi dans la noticeUniversité ou école supérieure
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Renewable Energy Research Center pays non établi dans la noticeStructure de recherche
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Graduate School of Arts and Sciences pays non établi dans la noticeUniversité ou école supérieure
Department of Chemical Science and Engineering — Tokyo Institute of Technology, Department of Chemistry and Life Science — Yokohama National University et National Institute of Advanced Industrial Science and Technology, avec 3 autres affiliations.
Une affiliation ne permet pas de déduire la nationalité d’un auteur.