2026-04-17T03:35:40Zhttps://recercat.cat/oai/request
oai:recercat.cat:10256/235842024-06-18T13:58:50Zcom_2072_452955com_2072_2054col_2072_453073
RECERCAT author Kasper, Johann B. author Saisaha, Pattama author Roo, Maurits de author Groen, Mitchell J. author Vicens Serra, Laia author Borrell Recasens, Margarida author Boer, Johannes W. de author Hage, Ronald author Costas Salgueiro, Miquel author Browne, Wesley R. 2024-06-18T13:58:50Z 2024-06-18T13:58:50Z 2023-01-09 http://hdl.handle.net/10256/23584 The mechanism and the reactive species involved in the oxidation of alkenes, and alcohols with H2O2, catalysed by an in situ prepared mixture of a MnII salt, pyridine-2-carboxylic acid and a ketone is elucidated using substrate competition experiments, kinetic isotope effect (KIE) measurements, and atom tracking with 18O labelling. The data indicate that a single reactive species engages in the oxidation of both alkenes and alcohols. The primary KIE in the oxidation of benzyl alcohols is ca. 3.5 and shows the reactive species to be selective despite a zero order dependence on substrate concentration, and the high turnover frequencies (up to 30 s−1) observed. Selective 18O labelling identifies the origin of the oxygen atoms transferred to the substrate during oxidation, and is consistent with a highly reactive, e. g., [MnV(O)(OH)] or [MnV(O)2], species rather than an alkylperoxy or hydroperoxy species Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess Oxidació Oxidation Alquens Alkenes A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion peer-reviewed