Autor segons l'article: Zhang, Teng; Sole-Daura, Albert; Fouilloux, Hugo; Poblet, Josep M.; Proust, Anna; Carbo, Jorge J.; Guillemot, Geoffroy;
Departament: Química Física i Inorgànica
e-ISSN: 1867-3899
Autor/s de la URV: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria / Solé Daura, Albert
Paraules clau: Titanium compounds Titanium complexes Titanium Silicates Repulsive interactions Product distributions Polyoxotungstates Polyoxometalates Oxidative dehydrogenation reactions Oxidation reactions Oxidation Olefins Mechanistic study Epoxidation reactions Epoxidation Dft Dehydrogenation Coordination reactions Computational studies Catalytic oxidation Catalyst activity Alkene epoxidation Alkene
Resum: Titanium complexes of silanol functionalized polyoxometalates (THA)(3)[SbW9O33(RSiO)(3)Ti((OPr)-Pr-i)] (Ti-SiloxPOMs) catalyze alkene oxidation with tert-butyl hydrogen peroxide (TBHP). However catalytic activity and product distribution in the oxidation of allylic alcohols are shown to depend on the steric surrounding generated by the SiloxPOM (R=Bu-t, Pr-i, Pr-n). Combined experimental and computational studies clarify how steric repulsions between the oxidant (Bu-t group) and the surrounding SiloxPOM govern the reaction pathways leading either to oxidation of the alcohol function (R=Bu-t) or to alkene epoxidation (R=Pr-n). Moreover, another consequence of this steric repulsive interactions is that outer-sphere mechanisms become competitive with the inner-sphere ones (coordination of allylic alcohol), whether for the oxidative dehydrogenation reaction or for the epoxidation reaction. In the case of unfunctionalized olefins (linear and cyclic), we show that reducing the bulkiness surrounding the active site leads to higher conversion to epoxide, emphasizing that these Ti-SiloxPOMs may behave as structural and functional models for metal single-site in Ti-Silicates.
Àrees temàtiques: Química Physical and theoretical chemistry Organic chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Engenharias i Ciências biológicas ii Ciências ambientais Ciências agrárias i Ciência de alimentos Chemistry, physical Catalysis Biotecnología Astronomia / física
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 1867-3880
Adreça de correu electrònic de l'autor: josepmaria.poblet@urv.cat j.carbo@urv.cat
Identificador de l'autor: 0000-0002-4533-0623 0000-0002-3945-6721
Data d'alta del registre: 2024-07-27
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cctc.202001779
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Chemcatchem. 13 (4): 1220-1229
Referència de l'ítem segons les normes APA: Zhang, Teng; Sole-Daura, Albert; Fouilloux, Hugo; Poblet, Josep M.; Proust, Anna; Carbo, Jorge J.; Guillemot, Geoffroy; (2021). Reaction Pathway Discrimination in Alkene Oxidation Reactions by Designed Ti-Siloxy-Polyoxometalates. Chemcatchem, 13(4), 1220-1229. DOI: 10.1002/cctc.202001779
DOI de l'article: 10.1002/cctc.202001779
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2021
Tipus de publicació: Journal Publications
Repositori URV