{ "dc.contributor.author": "Nuñez-Zarur, Francisco" , "dc.contributor.author": "Poater i Teixidor, Jordi" , "dc.contributor.author": "Rodríguez-Santiago, Luis" , "dc.contributor.author": "Solans Monfort, Xavier" , "dc.contributor.author": "Solà i Puig, Miquel" , "dc.contributor.author": "Sodupe Roure, Mariona" , "dc.date.accessioned": "2015-11-03T12:21:12Z" , "dc.date.available": "2015-11-03T12:21:12Z" , "dc.date.issued": "2012-09-15" , "dc.identifier.issn": "2210271X" , "dc.identifier.uri": "http://hdl.handle.net/10256/11420" , "dc.description.abstract": "Hoveyda-Grubbs complexes are commonly used catalysts in alkene metathesis. They are precursors of the catalytic species and need to be activated before entering into the real catalytic cycle. This activation can determine in a large extent the performance of the catalyst and thus, it is important to understand the factors that influence their activation and stability. In the present work, the electronic structure of 15 different Hoveyda-Grubbs precatalysts is analyzed by means of DFT quantum chemical calculations. Electronic delocalization measures and aromaticity indices have been used to study the influence of the Hoveyda ligand substituents on the Ru...O interaction and the metal carbene bond, and to analyze whether or not the 5-membered metal containing ring exhibits metalloaromaticity. Results show that these complexes do not exhibit any metalloaromaticity, although delocalization measures indicate that there is a certain π electron delocalization on the Hoveyda ligand. On the other hand, present study shows that the Ru...O interaction is mainly electrostatic and that the influence of the substituents not only depends on the changes occurred at the O atom but also on the metal site. Substituents para to the alkoxy group (meta to the carbene) mainly tune the electronic structure of the chelating ligand in such a way that electron donor substituents strengthen the Ru...O interaction whereas electron withdrawing ones induce the reverse effect. However, substituents in para to the carbene (meta to the alkoxy) mainly tune the electronic structure of the ruthenium carbene bond modifying the Ruδ-Ceneδ+ bond polarization and producing the opposite effect" , "dc.description.sponsorship": "We would like to thank the financial support from MICINN and the DIUE of the Generalitat de Catalunya through the CTQ2011-24847/BQU, CTQ2011-23156/BQU and CTQ2011-25086/BQU, and 2009SGR638, 2009SGR637 and 2009SGR528 Projects, respectively. FNZ wishes to thank to Universitat Autonoma de Barcelona for his PIF grant and JP and XSM also acknowledge the MICINN for their Ramon y Cajal contracts. Support for the research of M. Sola and M. Sodupe was received through the ICREA Academia 2009 and 2011, respectively, prizes for excellence in research funded by the DIUE of the Generalitat de Catalunya" , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.publisher": "Elsevier" , "dc.relation": "MICINN/PN 2012-2014/CTQ2011-23156" , "dc.relation": "MICINN/PN 2012-2014/CTQ2011-25086" , "dc.relation": "AGAUR/2009-2014/2009 SGR-637" , "dc.relation": "AGAUR/2009-2014/2009 SGR-528" , "dc.relation.isformatof": "Reproducció digital del document publicat a: http://dx.doi.org/10.1016/j.comptc.2012.07.015" , "dc.relation.ispartof": "© Computational and Theoretical Chemistry, 2012, vol. 996, p. 57-67" , "dc.relation.ispartofseries": "Articles publicats (D-Q)" , "dc.rights": "Tots els drets reservats" , "dc.subject": "Alquens" , "dc.subject": "Alkenes" , "dc.subject": "Metàtesi (Química)" , "dc.subject": "Metathesis (Chemistry)" , "dc.subject": "Funcional de densitat, Teoria del" , "dc.subject": "Density functionals" , "dc.subject": "Catalitzadors metàl·lics de transició" , "dc.subject": "Transition metal catalysts" , "dc.title": "On the electronic structure of second generation Hoveyda-Grubbs alkene metathesis precursors" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/embargoedAccess" , "dc.embargo.terms": "Cap" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" , "dc.identifier.doi": "http://dx.doi.org/10.1016/j.comptc.2012.07.015" , "dc.identifier.idgrec": "016475" , "dc.contributor.funder": "Ministerio de Ciencia e Innovación (Espanya)" , "dc.contributor.funder": "Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca" }