Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry
The new ligand 6-mercapto-2(1 H)-pyridone (H2PySO) has been prepared in good yield by reaction of 6-chloro-pyridin-2-ol with NaSH. Reaction of the salt K2PySO, generated in situ, with the appropriate complex [M(μ-C1)(diolefin)]2affords the tetranuclear complexes [M 4(μ-PySO)2(diolefin)4] [M = Rh, di...
| Autores: | , , , , , |
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| Tipo de documento: | artigo |
| Estado: | Versión aceptada para publicación |
| Data de publicação: | 2009 |
| País: | España |
| Recursos: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositório: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/133854 |
| Acesso em linha: | http://hdl.handle.net/10261/133854 |
| Access Level: | Acceso aberto |
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Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistryAlonso, Pablo J.Benedí, OscarFabra-Caro, María J.Lahoz, Fernando J.Oro, Luis A.Pérez-Torrente, Jesús J.The new ligand 6-mercapto-2(1 H)-pyridone (H2PySO) has been prepared in good yield by reaction of 6-chloro-pyridin-2-ol with NaSH. Reaction of the salt K2PySO, generated in situ, with the appropriate complex [M(μ-C1)(diolefin)]2affords the tetranuclear complexes [M 4(μ-PySO)2(diolefin)4] [M = Rh, diolefin = 1,5-cyclooctadiene (cod) (1), tetrafluorobenzobarralene (tfbb) (2); M = lr, diolefin = cod (3)]. The molecular structure of complex 1 has been determined by X-ray diffraction methods. The tetranuclear structure is supported by two S, N, Otridentate ligands exhibiting a 1κO, 2κN, 3:4κ2 S coordination mode. Carbonylation of the rhodium diolefin complexes at atmospheric pressure gives [Rh4(μ-PyS0)2(C0)8] (4). The carbonylation of 1 is partially reversible, and the mixed-ligand complex [Rh4(μ-PySO)2(cod)2(CO)4] (5) has been obtained as a single isomer. The reaction of 4 with triphenylphosphine gives the compound [Rh4(μ-PySO)2(CO)4(PPh 3)4] (6) which also exists as a single isomer of C 2 symmetry. The diolefin complexes are redox active and exhibit two one-electron oxidations at a platinum disk electrode in dichloromethane separated by approximately 0.5 V at potentials accessible by chemical oxidants. The tetranuclear complexes were selectively oxidized to the 63-electron mixed-valence cationic complexes [M4(μ-PySO)2(diolefin) 4]+(1a+, 2+, and 3+) by using AgCF3SO3 as oxidant and isolated as the triflate salts. Alternatively, the oxidation with [Cp2Fe]PF6 gives [Rh4(μ-PySO)2(cod)4][PF6] (1b+). The parameters obtained from the simulation of the electron paramagnetic resonance spectra of the oxidized species strongly suggest that the unpaired electron is delocalized over only two metal atoms in the complexes.The financial support from Ministerio de Educación y Ciencia (MEC/FEDER) Project CTQ2006-03973/BQU and Grant CSD2006-0015 Consolider Ingenio 2010 is gratefully acknowledged.Peer ReviewedAmerican Chemical SocietyMinisterio de Educación y Ciencia (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2016201620092016info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/133854reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1021/ic9005289Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1338542026-05-22T06:33:51Z |
| dc.title.none.fl_str_mv |
Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry |
| title |
Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry |
| spellingShingle |
Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry Alonso, Pablo J. |
| title_short |
Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry |
| title_full |
Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry |
| title_fullStr |
Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry |
| title_full_unstemmed |
Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry |
| title_sort |
Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry |
| dc.creator.none.fl_str_mv |
Alonso, Pablo J. Benedí, Oscar Fabra-Caro, María J. Lahoz, Fernando J. Oro, Luis A. Pérez-Torrente, Jesús J. |
| author |
Alonso, Pablo J. |
| author_facet |
Alonso, Pablo J. Benedí, Oscar Fabra-Caro, María J. Lahoz, Fernando J. Oro, Luis A. Pérez-Torrente, Jesús J. |
| author_role |
author |
| author2 |
Benedí, Oscar Fabra-Caro, María J. Lahoz, Fernando J. Oro, Luis A. Pérez-Torrente, Jesús J. |
| author2_role |
author author author author author |
| dc.contributor.none.fl_str_mv |
Ministerio de Educación y Ciencia (España) Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| description |
The new ligand 6-mercapto-2(1 H)-pyridone (H2PySO) has been prepared in good yield by reaction of 6-chloro-pyridin-2-ol with NaSH. Reaction of the salt K2PySO, generated in situ, with the appropriate complex [M(μ-C1)(diolefin)]2affords the tetranuclear complexes [M 4(μ-PySO)2(diolefin)4] [M = Rh, diolefin = 1,5-cyclooctadiene (cod) (1), tetrafluorobenzobarralene (tfbb) (2); M = lr, diolefin = cod (3)]. The molecular structure of complex 1 has been determined by X-ray diffraction methods. The tetranuclear structure is supported by two S, N, Otridentate ligands exhibiting a 1κO, 2κN, 3:4κ2 S coordination mode. Carbonylation of the rhodium diolefin complexes at atmospheric pressure gives [Rh4(μ-PyS0)2(C0)8] (4). The carbonylation of 1 is partially reversible, and the mixed-ligand complex [Rh4(μ-PySO)2(cod)2(CO)4] (5) has been obtained as a single isomer. The reaction of 4 with triphenylphosphine gives the compound [Rh4(μ-PySO)2(CO)4(PPh 3)4] (6) which also exists as a single isomer of C 2 symmetry. The diolefin complexes are redox active and exhibit two one-electron oxidations at a platinum disk electrode in dichloromethane separated by approximately 0.5 V at potentials accessible by chemical oxidants. The tetranuclear complexes were selectively oxidized to the 63-electron mixed-valence cationic complexes [M4(μ-PySO)2(diolefin) 4]+(1a+, 2+, and 3+) by using AgCF3SO3 as oxidant and isolated as the triflate salts. Alternatively, the oxidation with [Cp2Fe]PF6 gives [Rh4(μ-PySO)2(cod)4][PF6] (1b+). The parameters obtained from the simulation of the electron paramagnetic resonance spectra of the oxidized species strongly suggest that the unpaired electron is delocalized over only two metal atoms in the complexes. |
| publishDate |
2009 |
| dc.date.none.fl_str_mv |
2009 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/10261/133854 |
| url |
http://hdl.handle.net/10261/133854 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.relation.none.fl_str_mv |
http://dx.doi.org/10.1021/ic9005289 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) |
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Consejo Superior de Investigaciones Científicas (CSIC) |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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15.811543 |