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dc.contributor.authorPoater, Albert
dc.contributor.authorVummaleti, Sai V. C.
dc.contributor.authorPolo, Alfonso
dc.contributor.authorCavallo, Luigi
dc.date.accessioned2016-12-13T13:46:38Z
dc.date.available2016-12-13T13:46:38Z
dc.date.issued2016-09-14
dc.identifier.citationPoater A, Vummaleti SVC, Polo A, Cavallo L (2016) Clean and Selective Catalytic C-H alkylation of Alkenes with Environmental friendly Alcohols. Journal of Molecular Catalysis A: Chemical. Available: http://dx.doi.org/10.1016/j.molcata.2016.09.010.
dc.identifier.issn1381-1169
dc.identifier.doi10.1016/j.molcata.2016.09.010
dc.identifier.urihttp://hdl.handle.net/10754/622012
dc.description.abstractBearing 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 [Science2011, 333, 1613] allow the formation of a C-C 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 Csingle bondO 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 Csingle bondH 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.
dc.description.sponsorshipWe thank the helpful comments of the referees that have improved this manuscript. 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.
dc.publisherElsevier BV
dc.relation.urlhttp://www.sciencedirect.com/science/article/pii/S138111691630382X
dc.rightsNOTICE: this is the author’s version of a work that was accepted for publication in Journal of Molecular Catalysis A: Chemical. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Molecular Catalysis A: Chemical, 13 September 2016. DOI: 10.1016/j.molcata.2016.09.010
dc.subjecthomogeneous catalysis
dc.subjectruthenium catalysis
dc.subjectDFT calculations
dc.subjectgreen chemistry
dc.subjectalkene
dc.subjectC-H alkylation
dc.titleClean and Selective Catalytic C-H alkylation of Alkenes with Environmental friendly Alcohols
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalJournal of Molecular Catalysis A: Chemical
dc.eprint.versionPost-print
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17003 Girona, Catalonia, Spain
kaust.personVummaleti, Sai V. C.
kaust.personCavallo, Luigi
dc.date.published-online2016-09-14
dc.date.published-print2017-07


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