Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands

Four different pincer ligands, which prove that the disposition of the donor atoms in pincer ligands allows them to develop a marked ability to form less common coordination polyhedra and to favor unusual metal oxidation states, have been generated starting from OsH6(PiPr3)2 and 2-phenyl-6-(1H-pyraz...

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Autores: Alabau, Roberto G., Esteruelas, Miguel A., Oliván, Montserrat, Oñate, Enrique
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/149463
Acceso en línea:http://hdl.handle.net/10261/149463
Access Level:acceso abierto
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spelling Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligandsAlabau, Roberto G.Esteruelas, Miguel A.Oliván, MontserratOñate, EnriqueFour different pincer ligands, which prove that the disposition of the donor atoms in pincer ligands allows them to develop a marked ability to form less common coordination polyhedra and to favor unusual metal oxidation states, have been generated starting from OsH6(PiPr3)2 and 2-phenyl-6-(1H-pyrazol-3-yl)pyridine (Hpz-py-Ph) in order to stabilize phosphorescent, pentagonal-bipyramidal osmium(IV) emitters. Complex 1 reacts with the disubstituted heterocycle to give OsH2{κ3-N,N′,C-(pz-py-C6H4)}(PiPr3)2 (2), as a result of the activation of a phenyl o-CH bond and the pyrazolyl NH of the pyridine substituents. The addition of methyl trifluoromethanesulfonate (MeOTf) to 2 produces the methylation of the free N atom of the pz group and the formation of the salt [OsH2{κ3-N,N′,C-(Mepz-py-C6H4)}(PiPr3)2]OTf (3), which undergoes deprotonation of the metal center in the presence of KOtBu. The resulting monohydride OsH{κ3-N,N′,C-(Mepz-py-C6H4)}(PiPr3)2 (4) is unstable and evolves into OsH2{κ3-C,N,C′-(Mepz-py-C6H4)}(PiPr3)2 (5) as a consequence of the oxidative addition of the C–H bond at position 4 of the Mepz group to the osmium atom of 4. The addition of MeOTf to 5 produces the methylation of the free N atom of the Mepz group, which is converted into a remote N-heterocyclic carbene, to form [OsH2{κ3-C,N,C′-(Me2pz-py-C6H4)}(PiPr3)2]OTf (6). Complex 1 also reacts with 2-(1H-pyrazol-3-yl)pyridine (Hpz-py). The reaction gives rise to the trihydride derivative OsH3{κ2-N,N-(pz-py)}(PiPr3)2 (7), which leads to the salt [OsH3{κ2-N,N-(Mepz-py)}(PiPr3)2]OTf (8) by addition of MeOTf. The deprotonation of 8 affords the osmium(II) dihydride OsH2{κ2-N,N-(Mepz-py)}(PiPr3)2 (9), which is stable, in contrast to 4. Complexes 2, 3, 5, 7, and 8 are emissive in the green to red region upon photoexcitation.Financial support from the MINECO of Spain (Project CTQ2014-52799-P), the Diputación General de Aragón (E-35), FEDER, and the European Social Fund is acknowledged.Peer reviewedAmerican Chemical SocietyMinisterio de Economía y Competitividad (España)European CommissionDiputación General de AragónConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201720172017info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/149463reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-52799-Phttps://doi.org/10.1021/acs.organomet.7b00193Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1494632026-05-22T06:33:51Z
dc.title.none.fl_str_mv Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands
title Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands
spellingShingle Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands
Alabau, Roberto G.
title_short Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands
title_full Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands
title_fullStr Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands
title_full_unstemmed Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands
title_sort Preparation of phosphorescent osmium(IV) complexes with N,N′,C- and C,N,C′-pincer ligands
dc.creator.none.fl_str_mv Alabau, Roberto G.
Esteruelas, Miguel A.
Oliván, Montserrat
Oñate, Enrique
author Alabau, Roberto G.
author_facet Alabau, Roberto G.
Esteruelas, Miguel A.
Oliván, Montserrat
Oñate, Enrique
author_role author
author2 Esteruelas, Miguel A.
Oliván, Montserrat
Oñate, Enrique
author2_role author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (España)
European Commission
Diputación General de Aragón
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Four different pincer ligands, which prove that the disposition of the donor atoms in pincer ligands allows them to develop a marked ability to form less common coordination polyhedra and to favor unusual metal oxidation states, have been generated starting from OsH6(PiPr3)2 and 2-phenyl-6-(1H-pyrazol-3-yl)pyridine (Hpz-py-Ph) in order to stabilize phosphorescent, pentagonal-bipyramidal osmium(IV) emitters. Complex 1 reacts with the disubstituted heterocycle to give OsH2{κ3-N,N′,C-(pz-py-C6H4)}(PiPr3)2 (2), as a result of the activation of a phenyl o-CH bond and the pyrazolyl NH of the pyridine substituents. The addition of methyl trifluoromethanesulfonate (MeOTf) to 2 produces the methylation of the free N atom of the pz group and the formation of the salt [OsH2{κ3-N,N′,C-(Mepz-py-C6H4)}(PiPr3)2]OTf (3), which undergoes deprotonation of the metal center in the presence of KOtBu. The resulting monohydride OsH{κ3-N,N′,C-(Mepz-py-C6H4)}(PiPr3)2 (4) is unstable and evolves into OsH2{κ3-C,N,C′-(Mepz-py-C6H4)}(PiPr3)2 (5) as a consequence of the oxidative addition of the C–H bond at position 4 of the Mepz group to the osmium atom of 4. The addition of MeOTf to 5 produces the methylation of the free N atom of the Mepz group, which is converted into a remote N-heterocyclic carbene, to form [OsH2{κ3-C,N,C′-(Me2pz-py-C6H4)}(PiPr3)2]OTf (6). Complex 1 also reacts with 2-(1H-pyrazol-3-yl)pyridine (Hpz-py). The reaction gives rise to the trihydride derivative OsH3{κ2-N,N-(pz-py)}(PiPr3)2 (7), which leads to the salt [OsH3{κ2-N,N-(Mepz-py)}(PiPr3)2]OTf (8) by addition of MeOTf. The deprotonation of 8 affords the osmium(II) dihydride OsH2{κ2-N,N-(Mepz-py)}(PiPr3)2 (9), which is stable, in contrast to 4. Complexes 2, 3, 5, 7, and 8 are emissive in the green to red region upon photoexcitation.
publishDate 2017
dc.date.none.fl_str_mv 2017
2017
2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/149463
url http://hdl.handle.net/10261/149463
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-52799-P
https://doi.org/10.1021/acs.organomet.7b00193
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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