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Ministerio de Econom铆a y Competitividad (Espanya) | |
Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya Polo Ortiz, Alfonso Cavallo, Luigi |
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2017 July | |
Bearing the alkylation of alkene substrates using alcohol as solvent, catalysed by the cationic Ru-based catalyst [(C6H6)(PCy3)(CO)RuH]+, DFT calculations have been carried out to get mechanistic insights of such an environmental friendly reaction. Hard experimental conditions of Yi and coworkers [Science 2011, 333, 1613] allow the formation of a CC bond between indene and ethanol. The predicted mechanism suggests a cationic Ru-alkenyl species once two equivalents of indene interact releasing a molecule of indane subproduct. Then, oxidative addition of the CO bond of alcohol to Ru-alkenyl species leads to Ru-alkenyl-alkyl species, followed by the reductive elimination process produces the desired alkylation product and a Ru-hydroxo complex. Finally, vinylic CH activation and water elimination regenerates the Ru-alkenyl species. In this paper we present a full description of the complete reaction pathway along with possible alternative pathways, which are predicted to display higher upper barriers. Furthermore, the present study explains the possible reasons for the absence of undesired products such as indene dimer or hydroxylated indene in the experiments We thank King Abdullah University of Science and Technology (CFF project) for support. A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN |
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application/pdf | |
http://hdl.handle.net/10256/14335 | |
eng | |
Elsevier | |
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molcata.2016.09.010 info:eu-repo/semantics/altIdentifier/issn/1381-1169 info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/ |
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Tots els drets reservats | |
Alquilaci贸
Alkylation Funcional de densitat, Teoria del Density functionals Catalitzadors de rodi Rhodium catalyst |
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Clean and selective catalytic C-H alkylation of alkenes with environmental friendly alcohols | |
info:eu-repo/semantics/article | |
DUGiDocs |