Titre :

Gem-diols-type intermediate of ketone activation on sn-β zeolite as studied by solid-state nmr spectroscopy

Auteur(s) :

Qi, Guodong [Auteur]
University of Chinese Academy of Sciences [Beijing] [UCAS]
Chinese Academy of Sciences [Wuhan Branch]
Chu, Yueying [Auteur]
University of Chinese Academy of Sciences [Beijing] [UCAS]
Chinese Academy of Sciences [Wuhan Branch]
Wang, Qiang [Auteur]
University of Chinese Academy of Sciences [Beijing] [UCAS]
Chinese Academy of Sciences [Wuhan Branch]
Wang, Xingxing [Auteur]

Li, Yi [Auteur]

Trebosc, Julien [Auteur]
Université de Lille, Sciences et Technologies
Lafon, Olivier [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Xu, Jun [Auteur]
University of Chinese Academy of Sciences [Beijing] [UCAS]
Wuhan University of Science and Technology
Chinese Academy of Sciences [Wuhan Branch]
Deng, Feng [Auteur]
University of Chinese Academy of Sciences [Beijing] [UCAS]
Chinese Academy of Sciences [Wuhan Branch]

Titre de la revue :

Angewandte Chemie

Nom court de la revue :

Angew. Chem. Int. Ed. Engl.

Numéro :

59

Pagination :

19532-19538

Éditeur :

Wiley-VCH Verlag

Date de publication :

2020-05-25

ISSN :

1521-3773

Mot(s)-clé(s) en anglais :

biomass conversion
zeolites
ketones
carbonyl groups
solid-state NMR spectroscopy

Discipline(s) HAL :

Chimie/Catalyse
Chimie/Chimie inorganique

Résumé en anglais : [en]

Lewis acid zeolites have found increasing application in the field of biomass conversion, in which the selective transformation of carbonyl-containing molecules is of particular importance due to their relevance in organic ...
Lire la suite >Lewis acid zeolites have found increasing application in the field of biomass conversion, in which the selective transformation of carbonyl-containing molecules is of particular importance due to their relevance in organic synthesis. Mechanistic insight into the activation of carbonyl groups on Lewis acid sites is challenging and critical for the understanding of the catalytic process, which requires the identification of reaction intermediates. Here we report the observation of a stable surface gem-diol-type species in the activation of acetone on Sn-β zeolite. 13 C, 119 Sn, and 13 C-119 Sn double-resonance NMR spectroscopic studies demonstrate that only the open Sn site ((SiO)3 Sn-OH) on Sn-β is responsible for the formation of the surface species. 13 C MAS NMR experiments together with density functional theory calculations suggest that the gem-diol-type species exhibits high reactivity and can serve as an active intermediate in the Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction of acetone with cyclohexanol. The gem-diol-type species offers an energy-preferable pathway for the direct carbon-to-carbon hydrogen transfer between ketone and alcohol. The results provide new insights into the transformation of carbonyl-containing molecules catalyzed by Lewis acid zeolites.Lire moins >

Langue :

Anglais

Audience :

Internationale

Vulgarisation :

Non

Autre(s) projet(s) ou source(s) de financement :

The National Natural Science Foundation of China (Grants 21872170, U1932218, 22061130202, 21733013, 91745111)
Key projects of international partnership plan for foreign cooperation (112942KYSB20180009)
key program for frontier science of the Chinese Academy of Sciences (QYZDB-SSW-SLH027)
Hubei Provincial Natural Science Foundation (2017CFA032)

Établissement(s) :

CNRS
Centrale Lille
ENSCL
Univ. Artois
Université de Lille

Collections :

• Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181

Équipe(s) de recherche :

RMN et matériaux inorganiques (RM2I)

Date de dépôt :

2022-03-02T07:14:46Z
2023-11-12T16:55:32Z
2023-11-17T14:45:49Z