En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands

Synthetic routes for ruthenium(II) complexes bearing the {Ru(¿4C, N, N', P-L)} fragment (L = tripodal tetradentate ligand) are explored. Tripodal ligands LH1-LH3 diastereoselectively react with the dimer [{(Cy)RuCl}2(µ-Cl)2] (Cy = ¿6-p-MeC6H4iPr), affording the p-cymene compounds [(Cy)Ru(¿3N, N...

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Autores: Téllez, Juan, Méndez, Isabel, Viguri, Fernando, Rodríguez, Ricardo, Lahoz, Ferenando J., García-Orduña, Pilar, Carmona, Daniel
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:84364
Acceso en línea:http://zaguan.unizar.es/record/84364
Access Level:acceso abierto
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network_acronym_str ES
network_name_str España
repository_id_str
spelling En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate LigandsTéllez, JuanMéndez, IsabelViguri, FernandoRodríguez, RicardoLahoz, Ferenando J.García-Orduña, PilarCarmona, DanielSynthetic routes for ruthenium(II) complexes bearing the {Ru(¿4C, N, N', P-L)} fragment (L = tripodal tetradentate ligand) are explored. Tripodal ligands LH1-LH3 diastereoselectively react with the dimer [{(Cy)RuCl}2(µ-Cl)2] (Cy = ¿6-p-MeC6H4iPr), affording the p-cymene compounds [(Cy)Ru(¿3N, N', P-LH)][SbF6] (1-3). Refluxing complexes 1-3 in MeCN gives [Ru(¿3N, N', P-LH)(NCMe)3][SbF6]2 (4a-6a). In refluxing MeOH, isomers 4a-6a evolve to the corresponding mer complexes 4c-6c. Reaction of [RuCl2(PPh3)3] with LH1 affords [RuCl2(PPh3)(¿3N, N', P-LH1)] (7) as only one isomer. [RuClH(CO)(PPh3)3] reacts with ligands LH1-LH3 to give [RuH(CO)(PPh3)(¿3N, N', P-LH)]Cl (8-10). Complexes 8-10 were isolated as a mixture of only two diastereomers as pairs of enantiomers. Refluxing suspensions of complexes 8-10 in 2-ethoxyethanol afforded the corresponding metalated complexes [RuCl(CO)(¿4C, N, N', P-L)] (11-13), in which the tripodal ligands L1-L3 act as tetradentate ligands. Only one stereoisomer was detected for complexes 11 and 13, but metalation at the C-2 or C-6 carbons gave a mixture of two isomers for complex 12. The new complexes have been characterized by analytical and spectroscopic means and by the determination of the crystal structures of the complexes 1, 2, 5c, 10a, 11a, 12a, b, and 13a by X-ray diffractometry.2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://zaguan.unizar.es/record/84364reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2015-66079-Pinfo:eu-repo/grantAgreement/ES/MINECO/RYC-2013-13800info:eu-repo/semantics/openAccessoai:zaguan.unizar.es:843642026-05-29T13:59:51Z
dc.title.none.fl_str_mv En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands
title En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands
spellingShingle En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands
Téllez, Juan
title_short En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands
title_full En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands
title_fullStr En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands
title_full_unstemmed En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands
title_sort En Route to Chiral-at-Metal Ruthenium Complexes Containing Tripodal Tetradentate Ligands
dc.creator.none.fl_str_mv Téllez, Juan
Méndez, Isabel
Viguri, Fernando
Rodríguez, Ricardo
Lahoz, Ferenando J.
García-Orduña, Pilar
Carmona, Daniel
author Téllez, Juan
author_facet Téllez, Juan
Méndez, Isabel
Viguri, Fernando
Rodríguez, Ricardo
Lahoz, Ferenando J.
García-Orduña, Pilar
Carmona, Daniel
author_role author
author2 Méndez, Isabel
Viguri, Fernando
Rodríguez, Ricardo
Lahoz, Ferenando J.
García-Orduña, Pilar
Carmona, Daniel
author2_role author
author
author
author
author
author
description Synthetic routes for ruthenium(II) complexes bearing the {Ru(¿4C, N, N', P-L)} fragment (L = tripodal tetradentate ligand) are explored. Tripodal ligands LH1-LH3 diastereoselectively react with the dimer [{(Cy)RuCl}2(µ-Cl)2] (Cy = ¿6-p-MeC6H4iPr), affording the p-cymene compounds [(Cy)Ru(¿3N, N', P-LH)][SbF6] (1-3). Refluxing complexes 1-3 in MeCN gives [Ru(¿3N, N', P-LH)(NCMe)3][SbF6]2 (4a-6a). In refluxing MeOH, isomers 4a-6a evolve to the corresponding mer complexes 4c-6c. Reaction of [RuCl2(PPh3)3] with LH1 affords [RuCl2(PPh3)(¿3N, N', P-LH1)] (7) as only one isomer. [RuClH(CO)(PPh3)3] reacts with ligands LH1-LH3 to give [RuH(CO)(PPh3)(¿3N, N', P-LH)]Cl (8-10). Complexes 8-10 were isolated as a mixture of only two diastereomers as pairs of enantiomers. Refluxing suspensions of complexes 8-10 in 2-ethoxyethanol afforded the corresponding metalated complexes [RuCl(CO)(¿4C, N, N', P-L)] (11-13), in which the tripodal ligands L1-L3 act as tetradentate ligands. Only one stereoisomer was detected for complexes 11 and 13, but metalation at the C-2 or C-6 carbons gave a mixture of two isomers for complex 12. The new complexes have been characterized by analytical and spectroscopic means and by the determination of the crystal structures of the complexes 1, 2, 5c, 10a, 11a, 12a, b, and 13a by X-ray diffractometry.
publishDate 2018
dc.date.none.fl_str_mv 2018
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/84364
url http://zaguan.unizar.es/record/84364
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-66079-P
info:eu-repo/grantAgreement/ES/MINECO/RYC-2013-13800
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv
publisher.none.fl_str_mv
dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
repository.name.fl_str_mv
repository.mail.fl_str_mv
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