Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds

The tetranuclear complexes [M4(μ-PyS2)2(diolefin)4] [PyS2 = 2,6-pyridinedithiolate; M = Rh, diolefin = cod (1,5-cyclooctadiene) (1), tfbb (tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene) (2); M = Ir, diolefin = cod (3), tfbb (4)] exhibit two one-electron oxidations at a platinum disk electrode...

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Autores: Casado, Miguel A., Pérez-Torrente, Jesús J., López, José A., Ciriano, Miguel A., Alonso, Pablo J., Lahoz, Fernando J., Oro, Luis A.
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2001
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/133827
Acesso em linha:http://hdl.handle.net/10261/133827
Access Level:acceso abierto
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spelling Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compoundsCasado, Miguel A.Pérez-Torrente, Jesús J.López, José A.Ciriano, Miguel A.Alonso, Pablo J.Lahoz, Fernando J.Oro, Luis A.The tetranuclear complexes [M4(μ-PyS2)2(diolefin)4] [PyS2 = 2,6-pyridinedithiolate; M = Rh, diolefin = cod (1,5-cyclooctadiene) (1), tfbb (tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene) (2); M = Ir, diolefin = cod (3), tfbb (4)] exhibit two one-electron oxidations at a platinum disk electrode in dichloromethane at potentials accessible by chemical reagents. The rhodium tetranuclear complexes were selectively oxidized to the monocationic complexes [Rh4(μ-PyS2)2(diolefin)4] + (1+, 2+) by mild one-electron oxidants such as [Cp2Fe]+ or [N(C6H4Br-4)3]+ and isolated as the PF6 -, BF4 -, and ClO4 - salts. Silver salts behave as noninnocent one-electron oxidants for the reactions with the rhodium complexes 1 and 2 since they give sparingly soluble coordination polymers. The complex [Ir4(μ-PyS2)2(cod)4] + (3+) was obtained as the tetrafluoroborate salt by reaction of 3 with 1 molar equiv of AgBF4, but the related complex 4+ could not be isolated from the chemical oxidation of [Ir4(μ-PyS2)2(tfbb)4] (4) with AgBF4. Oxidation of 3 and 4 with 2 molar equiv of common silver salts resulted in the fragmentation of the complexes to give the diamagnetic triiridium cations [Ir3(μ-PyS2)2(diolefin)3] +. The molecular structure of [Ir3(μ-PyS2)2(cod)3]BF 4, determined by X-ray diffraction methods, showed the three metal atoms within an angular arrangement. Both 2,6-pyridinedithiolate tridentate ligands bridge two metal-metal bonded d7 centers in pseudo octahedral environments and one d8 square-planar iridium center. An interpretation of the EPR spectra of the 63-electron mixed-valence paramagnetic tetranuclear complexes suggests that the unpaired electron is delocalized over two of the metal atoms in the complexes 1+-3+.The generous financial support from Dirección General de Enseñanza Superior e Investigación (DGES) (Projects PB98-641 and PB94-1186), and a fellowship (M. A. Casado) are gratefully acknowledged.Peer ReviewedAmerican Chemical SocietyMinisterio de Educación y Cultura (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2016201620012016info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/133827reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1021/ic001349qSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1338272026-05-22T06:33:51Z
dc.title.none.fl_str_mv Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds
title Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds
spellingShingle Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds
Casado, Miguel A.
title_short Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds
title_full Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds
title_fullStr Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds
title_full_unstemmed Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds
title_sort Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds
dc.creator.none.fl_str_mv Casado, Miguel A.
Pérez-Torrente, Jesús J.
López, José A.
Ciriano, Miguel A.
Alonso, Pablo J.
Lahoz, Fernando J.
Oro, Luis A.
author Casado, Miguel A.
author_facet Casado, Miguel A.
Pérez-Torrente, Jesús J.
López, José A.
Ciriano, Miguel A.
Alonso, Pablo J.
Lahoz, Fernando J.
Oro, Luis A.
author_role author
author2 Pérez-Torrente, Jesús J.
López, José A.
Ciriano, Miguel A.
Alonso, Pablo J.
Lahoz, Fernando J.
Oro, Luis A.
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Educación y Cultura (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The tetranuclear complexes [M4(μ-PyS2)2(diolefin)4] [PyS2 = 2,6-pyridinedithiolate; M = Rh, diolefin = cod (1,5-cyclooctadiene) (1), tfbb (tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene) (2); M = Ir, diolefin = cod (3), tfbb (4)] exhibit two one-electron oxidations at a platinum disk electrode in dichloromethane at potentials accessible by chemical reagents. The rhodium tetranuclear complexes were selectively oxidized to the monocationic complexes [Rh4(μ-PyS2)2(diolefin)4] + (1+, 2+) by mild one-electron oxidants such as [Cp2Fe]+ or [N(C6H4Br-4)3]+ and isolated as the PF6 -, BF4 -, and ClO4 - salts. Silver salts behave as noninnocent one-electron oxidants for the reactions with the rhodium complexes 1 and 2 since they give sparingly soluble coordination polymers. The complex [Ir4(μ-PyS2)2(cod)4] + (3+) was obtained as the tetrafluoroborate salt by reaction of 3 with 1 molar equiv of AgBF4, but the related complex 4+ could not be isolated from the chemical oxidation of [Ir4(μ-PyS2)2(tfbb)4] (4) with AgBF4. Oxidation of 3 and 4 with 2 molar equiv of common silver salts resulted in the fragmentation of the complexes to give the diamagnetic triiridium cations [Ir3(μ-PyS2)2(diolefin)3] +. The molecular structure of [Ir3(μ-PyS2)2(cod)3]BF 4, determined by X-ray diffraction methods, showed the three metal atoms within an angular arrangement. Both 2,6-pyridinedithiolate tridentate ligands bridge two metal-metal bonded d7 centers in pseudo octahedral environments and one d8 square-planar iridium center. An interpretation of the EPR spectra of the 63-electron mixed-valence paramagnetic tetranuclear complexes suggests that the unpaired electron is delocalized over two of the metal atoms in the complexes 1+-3+.
publishDate 2001
dc.date.none.fl_str_mv 2001
2016
2016
2016
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/10261/133827
url http://hdl.handle.net/10261/133827
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv http://dx.doi.org/10.1021/ic001349q
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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