Autor según el artículo: Mazloomi Z; Pretorius R; Pàmies O; Albrecht M; Diéguez M
Departamento: Química Física i Inorgànica Química Física i Inorgànica
Autor/es de la URV: Diéguez Fernández, Montserrat / Pamies Ollé, Oscar
Palabras clave: Clean water and sanitation
Resumen: © 2017 American Chemical Society. A set of iridium(I) and iridium(III) complexes is reported with triazolylidene ligands that contain pendant benzoxazole, thiazole, and methyl ether groups as potentially chelating donor sites. The bonding mode of these groups was identified by NMR spectroscopy and X-ray structure analysis. The complexes were evaluated as catalyst precursors in transfer hydrogenation and in acceptorless alcohol oxidation. High-valent iridium(III) complexes were identified as the most active precursors for the oxidative alcohol dehydrogenation, while a low-valent iridium(I) complex with a methyl ether functionality was most active in reductive transfer hydrogenation. This catalyst precursor is highly versatile and efficiently hydrogenates ketones, aldehydes, imines, allylic alcohols, and most notably also unpolarized olefins, a notoriously difficult substrate for transfer hydrogenation. Turnover frequencies up to 260 h-1were recorded for olefin hydrogenation, whereas hydrogen transfer to ketones and aldehydes reached maximum turnover frequencies greater than 2000 h-1. Mechanistic investigations using a combination of isotope labeling experiments, kinetic isotope effect measurements, and Hammett parameter correlations indicate that the turnover-limiting step is hydride transfer from the metal to the substrate in transfer hydrogenation, while in alcohol dehydrogenation, the limiting step is substrate coordination to the metal center.
Áreas temáticas: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 00201669
Direcció de correo del autor: oscar.pamies@urv.cat montserrat.dieguez@urv.cat
Identificador del autor: 0000-0002-2352-8508 0000-0002-8450-0656
Página final: 11298
Fecha de alta del registro: 2024-11-16
Volumen de revista: 56
Versión del articulo depositado: info:eu-repo/semantics/submittedVersion
Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.7b01707
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Inorganic Chemistry. 56 (18): 11282-11298
Referencia de l'ítem segons les normes APA: Mazloomi Z; Pretorius R; Pàmies O; Albrecht M; Diéguez M (2017). Triazolylidene Iridium Complexes for Highly Efficient and Versatile Transfer Hydrogenation of C=O, C=N, and C=C Bonds and for Acceptorless Alcohol Oxidation. Inorganic Chemistry, 56(18), 11282-11298. DOI: 10.1021/acs.inorgchem.7b01707
DOI del artículo: 10.1021/acs.inorgchem.7b01707
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2017
Página inicial: 11282
Tipo de publicación: Journal Publications