Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands

Treatment of complex Cp2TiCl2] with the lithium salt of 2-hydroxypyridine afforded complex Cp2Ti(Opy)2] (1), whereas the same synthetic strategy applied to the analogous zirconium compound Cp2ZrCl2] did not worked. However, the use of the metallocene Cptt 2ZrMe2] with protic ligands allowed directin...

Descripción completa

Detalles Bibliográficos
Autores: Casado, M.A., Álvarez-Vergara, M.C., Pérez-Torrente, J.J., Lahoz, F.J., Dobrinovich, I.T., Oro, L.A.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2015
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:60633
Acceso en línea:http://zaguan.unizar.es/record/60633
Access Level:acceso abierto
id ES_c47106c2f4fa687fe2db6d0fdf7a59f5
oai_identifier_str oai:zaguan.unizar.es:60633
network_acronym_str ES
network_name_str España
repository_id_str
spelling Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate LigandsCasado, M.A.Álvarez-Vergara, M.C.Pérez-Torrente, J.J.Lahoz, F.J.Dobrinovich, I.T.Oro, L.A.Treatment of complex Cp2TiCl2] with the lithium salt of 2-hydroxypyridine afforded complex Cp2Ti(Opy)2] (1), whereas the same synthetic strategy applied to the analogous zirconium compound Cp2ZrCl2] did not worked. However, the use of the metallocene Cptt 2ZrMe2] with protic ligands allowed directing the reactivity towards protonation of the methyl groups attached to zirconium. To check this approach we reacted Cptt 2ZrMe2] with methanol affording complex Cptt 2ZrMe(OMe)] (2), which was characterized in situ by NMR techniques. In the same line, the reaction of Cptt 2ZrMe2] with 2-hydroxypyridine gave complex Cptt 2Zr(Me)(Opy)] (3)//forcing the conditions of this reaction did not lead to the expected complex Cptt 2Zr(Opy)2], most probably due to the steric hindrance exerted by the bulky cyclopentadienyl ligands. Further reactions of complex 3 with ligands having acidic protons also led to the recovery of the starting complex. However, when shifting to the bifunctional ligand 2, 6-dimercaptopyridine py(SH)2] a double protonation of the methyl ligands in Cptt 2ZrMe2] occurred, allowing the isolation of mononuclear complex Cptt 2Zr(¿S, ¿S, ¿N-pyS2)] (4), upon evolution of methane. The molecular structure of complex 4 was determined by X-ray methods, showing the zirconium atom in a highly distorted trigonal bipyramidal arrangement//structural parameters indicate a conventional Zr-N bond, but rather weak Zr-S interactions.2015info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://zaguan.unizar.es/record/60633reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/DGA/E07info:eu-repo/grantAgreement/ES/DGA/E70info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenioinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2012–35665info:eu-repo/grantAgreement/ES/MINECO/CTQ2013-42532-Pinfo:eu-repo/semantics/openAccessoai:zaguan.unizar.es:606332026-05-29T13:59:51Z
dc.title.none.fl_str_mv Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands
title Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands
spellingShingle Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands
Casado, M.A.
title_short Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands
title_full Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands
title_fullStr Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands
title_full_unstemmed Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands
title_sort Synthesis of Titanium and Zirconium Complexes with 2-Pyridonate and 2, 6-Pyridinedithiolate Ligands
dc.creator.none.fl_str_mv Casado, M.A.
Álvarez-Vergara, M.C.
Pérez-Torrente, J.J.
Lahoz, F.J.
Dobrinovich, I.T.
Oro, L.A.
author Casado, M.A.
author_facet Casado, M.A.
Álvarez-Vergara, M.C.
Pérez-Torrente, J.J.
Lahoz, F.J.
Dobrinovich, I.T.
Oro, L.A.
author_role author
author2 Álvarez-Vergara, M.C.
Pérez-Torrente, J.J.
Lahoz, F.J.
Dobrinovich, I.T.
Oro, L.A.
author2_role author
author
author
author
author
description Treatment of complex Cp2TiCl2] with the lithium salt of 2-hydroxypyridine afforded complex Cp2Ti(Opy)2] (1), whereas the same synthetic strategy applied to the analogous zirconium compound Cp2ZrCl2] did not worked. However, the use of the metallocene Cptt 2ZrMe2] with protic ligands allowed directing the reactivity towards protonation of the methyl groups attached to zirconium. To check this approach we reacted Cptt 2ZrMe2] with methanol affording complex Cptt 2ZrMe(OMe)] (2), which was characterized in situ by NMR techniques. In the same line, the reaction of Cptt 2ZrMe2] with 2-hydroxypyridine gave complex Cptt 2Zr(Me)(Opy)] (3)//forcing the conditions of this reaction did not lead to the expected complex Cptt 2Zr(Opy)2], most probably due to the steric hindrance exerted by the bulky cyclopentadienyl ligands. Further reactions of complex 3 with ligands having acidic protons also led to the recovery of the starting complex. However, when shifting to the bifunctional ligand 2, 6-dimercaptopyridine py(SH)2] a double protonation of the methyl ligands in Cptt 2ZrMe2] occurred, allowing the isolation of mononuclear complex Cptt 2Zr(¿S, ¿S, ¿N-pyS2)] (4), upon evolution of methane. The molecular structure of complex 4 was determined by X-ray methods, showing the zirconium atom in a highly distorted trigonal bipyramidal arrangement//structural parameters indicate a conventional Zr-N bond, but rather weak Zr-S interactions.
publishDate 2015
dc.date.none.fl_str_mv 2015
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/60633
url http://zaguan.unizar.es/record/60633
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/DGA/E07
info:eu-repo/grantAgreement/ES/DGA/E70
info:eu-repo/grantAgreement/ES/MINECO/Consolider-Ingenio
info:eu-repo/grantAgreement/ES/MINECO/CTQ2012–35665
info:eu-repo/grantAgreement/ES/MINECO/CTQ2013-42532-P
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
_version_ 1869418881303445504
score 15.301603

Similares en LA Referencia