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Selective Oxidation of Glycerol via Acceptorless Dehydrogenation Driven by Ir(I)-NHC Catalysts
Iridium(I) compounds featuring bridge-functionalized bis-NHC ligands (NHC = N-heterocyclic carbene), [Ir(cod)(bis-NHC)] and [Ir(CO)(2)(bis-NHC)], have been prepared from the appropriate carboxylate- or hydroxy-functionalized bis-imidazolium salts. The related complexes [Ir(cod)(NHC)(2)](+) and [IrCl...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9696977/ https://www.ncbi.nlm.nih.gov/pubmed/36431768 http://dx.doi.org/10.3390/molecules27227666 |
Sumario: | Iridium(I) compounds featuring bridge-functionalized bis-NHC ligands (NHC = N-heterocyclic carbene), [Ir(cod)(bis-NHC)] and [Ir(CO)(2)(bis-NHC)], have been prepared from the appropriate carboxylate- or hydroxy-functionalized bis-imidazolium salts. The related complexes [Ir(cod)(NHC)(2)](+) and [IrCl(cod)(NHC)(cod)] have been synthesized from a 3-hydroxypropyl functionalized imidazolium salt. These complexes have been shown to be robust catalysts in the oxidative dehydrogenation of glycerol to lactate (LA) with dihydrogen release. High activity and selectivity to LA were achieved in an open system under low catalyst loadings using KOH as a base. The hydroxy-functionalized bis-NHC catalysts are much more active than both the carboxylate-functionalized ones and the unbridged bis-NHC iridium(I) catalyst with hydroxyalkyl-functionalized NHC ligands. In general, carbonyl complexes are more active than the related 1,5-cyclooctadiene ones. The catalyst [Ir(CO)(2){(MeImCH(2))(2)CHOH}]Br exhibits the highest productivity affording TONs to LA up to 15,000 at very low catalyst loadings. |
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