2026-04-13T05:02:59Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/235842024-06-18T13:58:50Zcom_2072_452955com_2072_2054col_2072_453073

00925njm 22002777a 4500 dc 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. author 2023-01-09 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 http://hdl.handle.net/10256/23584 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