Autor según el artículo: Zhang, Teng; Sole-Daura, Albert; Fouilloux, Hugo; Poblet, Josep M.; Proust, Anna; Carbo, Jorge J.; Guillemot, Geoffroy;

Departamento: Química Física i Inorgànica

e-ISSN: 1867-3899

Autor/es de la URV: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria

Palabras clave: 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

Resumen: 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.

Áreas temáticas: 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

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 1867-3880

Direcció de correo del autor: j.carbo@urv.cat josepmaria.poblet@urv.cat

Identificador del autor: 0000-0002-3945-6721 0000-0002-4533-0623

Fecha de alta del registro: 2023-03-06

Versión del articulo depositado: info:eu-repo/semantics/publishedVersion

Enlace a la fuente original: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cctc.202001779

URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/

Referencia al articulo segun fuente origial: Chemcatchem. 13 (4): 1220-1229

Referencia 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 del artículo: 10.1002/cctc.202001779

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2021

Tipo de publicación: Journal Publications