Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis
dc.contributor.author | Pump, Eva | |
dc.contributor.author | Slugovc, Christian | |
dc.contributor.author | Cavallo, Luigi | |
dc.contributor.author | Poater, Albert | |
dc.date.accessioned | 2015-08-19T12:23:34Z | |
dc.date.available | 2015-08-19T12:23:34Z | |
dc.date.issued | 2015-06-30 | |
dc.identifier.citation | Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis 2015, 34 (13):3107 Organometallics | |
dc.identifier.issn | 0276-7333 | |
dc.identifier.issn | 1520-6041 | |
dc.identifier.doi | 10.1021/om501246q | |
dc.identifier.uri | http://hdl.handle.net/10754/575254 | |
dc.description.abstract | The intramolecular allenylidene RuCl2(PR3)2(C═C═CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C–H activation was shown to be unfavored for energy barriers up to 70 kcal/mol. Thus, it turned out to be HCl (or other acid) that plays a crucial role during formation of the indenylidene, as the upper energy barrier decreases to a reasonable 35 kcal/mol. Moreover, we proved computationally that depending on the nature of the phosphine the intramolecular rearrangement is either facilitated (PPh3) or slightly hampered (PCy3), which is in line with experimental results. | |
dc.language.iso | en | |
dc.publisher | American Chemical Society (ACS) | |
dc.relation.url | http://pubs.acs.org/doi/abs/10.1021/om501246q | |
dc.rights | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/om501246q. | |
dc.subject | Olefin Metathesis | |
dc.subject | Mechanism | |
dc.subject | Computational studies | |
dc.subject | DFT | |
dc.subject | Ruthenium | |
dc.subject | Indenylidene | |
dc.subject | Allenylidene | |
dc.title | Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis | |
dc.type | Article | |
dc.contributor.department | Chemical Science Program | |
dc.contributor.department | KAUST Catalysis Center (KCC) | |
dc.contributor.department | Physical Science and Engineering (PSE) Division | |
dc.identifier.journal | Organometallics | |
dc.eprint.version | Post-print | |
dc.contributor.institution | Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, A-8010 Graz, Austria | |
dc.contributor.institution | Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia, Spain | |
dc.contributor.affiliation | King Abdullah University of Science and Technology (KAUST) | |
kaust.person | Pump, Eva | |
kaust.person | Cavallo, Luigi | |
refterms.dateFOA | 2016-06-30T00:00:00Z | |
dc.date.published-online | 2015-06-30 | |
dc.date.published-print | 2015-07-13 |
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