Author, as appears in the article.: Zhang, Teng; Sole-Daura, Albert; Fouilloux, Hugo; Poblet, Josep M.; Proust, Anna; Carbo, Jorge J.; Guillemot, Geoffroy;
Department: Química Física i Inorgànica
e-ISSN: 1867-3899
URV's Author/s: Carbó Martin, Jorge Juan / Poblet Rius, Josep Maria / Solé Daura, Albert
Keywords: 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
Abstract: 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.
Thematic Areas: 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
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 1867-3880
Author's mail: josepmaria.poblet@urv.cat j.carbo@urv.cat
Author identifier: 0000-0002-4533-0623 0000-0002-3945-6721
Record's date: 2024-07-27
Papper version: info:eu-repo/semantics/publishedVersion
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Chemcatchem. 13 (4): 1220-1229
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
Entity: Universitat Rovira i Virgili
Journal publication year: 2021
Publication Type: Journal Publications
Repositori URV