{ "dc.contributor.author": "Manzini, Simone" , "dc.contributor.author": "Poater Teixidor, Albert" , "dc.contributor.author": "Nelson, David J." , "dc.contributor.author": "Cavallo, Luigi" , "dc.contributor.author": "Nolan, Steven P." , "dc.date.accessioned": "2015-05-05T07:13:35Z" , "dc.date.available": "2015-05-05T07:13:35Z" , "dc.date.issued": "2014" , "dc.identifier.issn": "2041-6520" , "dc.identifier.uri": "http://hdl.handle.net/10256/10350" , "dc.description.abstract": "[RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25-0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3) 2] and [RuCl(η5-indenyl)(PPh3) 2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols" , "dc.description.sponsorship": "We thank the ERC (Advanced Investigator Award ` FUNCAT' to SPN) and the EPSRC for funding. Umicore is thanked for gi. s of materials. SPN is a Royal Society Wolfson Merit Award holder. Melanja Smith and Dr Tomas Lebl are thanked for assistance with NMR spectroscopy facilities. Dr Cesar A. Urbina-Blanco is acknowledged for useful discussions. LC thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici (Italy) for access to remarkable computational resources. AP thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226) and European Commission for a Career Integration Grant (CIG09-GA-2011-293900)" , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.publisher": "Royal Society of Chemistry (RSC)" , "dc.relation": "info:eu-repo/grantAgreement/MICINN//RYC-2009-05226/ES/RYC-2009-05226/" , "dc.relation.isformatof": "Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c3sc52612g" , "dc.relation.ispartof": "© Chemical Science, 2014, vol. 5, p. 180-188" , "dc.relation.ispartofseries": "Articles publicats (D-Q)" , "dc.rights": "Reconeixement 3.0 Espanya" , "dc.rights.uri": "http://creativecommons.org/licenses/by/3.0/es/deed.ca" , "dc.subject": "Isomerització" , "dc.subject": "Isomerization" , "dc.subject": "Ruteni" , "dc.subject": "Ruthenium" , "dc.subject": "Mecanismes de reacció (Química)" , "dc.subject": "Reaction mechanisms (Chemistry)" , "dc.subject": "Funcional de densitat, Teoria del" , "dc.subject": "Density functionals" , "dc.subject": "Catalitzadors" , "dc.subject": "Catalysts" , "dc.title": "How phenyl makes a difference: Mechanistic insights into the ruthenium(ii)-catalysed isomerisation of allylic alcohols" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/openAccess" , "dc.embargo.terms": "Cap" , "dc.relation.projectID": "info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" , "dc.identifier.doi": "http://dx.doi.org/10.1039/c3sc52612g" , "dc.identifier.idgrec": "020510" , "dc.contributor.funder": "Ministerio de Ciencia e Innovación (Espanya)" , "dc.relation.FundingProgramme": "FP7" , "dc.relation.ProjectAcronym": "COMPUTEDRUG" , "dc.identifier.eissn": "2041-6539" }