Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers
New 1,2-azolylamidino complexes cis-[Ru(bipy)2(NH=C(R)az*-κ2N,N)](OTf)2 (R = Me, Ph; az∗ = pz, indz, dmpz) are synthesized via chloride abstraction after a subsequent base-catalyzed coupling of a nitrile with the previously coordinated 1,2-azole. The synthetic procedure allows the easy obtainment of...
| Autores: | , , , , , , , , |
|---|---|
| Formato: | artículo |
| Fecha de publicación: | 2021 |
| País: | España |
| Recursos: | Universidad Autónoma de Madrid |
| Repositorio: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Idioma: | inglés |
| OAI Identifier: | oai:repositorio.uam.es:10486/704759 |
| Acesso em linha: | http://hdl.handle.net/10486/704759 https://dx.doi.org/10.1021/acs.inorgchem.0c03389 |
| Access Level: | acceso abierto |
| Palavra-chave: | Catalytic Performance Chloride Abstraction Electrochemical Studies Oxidation Reactions Photocatalytic Oxidations Photophysical Studies Ruthenium Complexes Synthetic Procedures Química |
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Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of ThioethersCuéllar, ElenaDiez-Varga, AlbertoTorroba, TomásDomingo-Legarda, PabloAlemán Lara, José JuliánCabrera Herranz, SilviaMartín-Alvarez, Jose M.Miguel, DanielVillafañe, FernandoCatalytic PerformanceChloride AbstractionElectrochemical StudiesOxidation ReactionsPhotocatalytic OxidationsPhotophysical StudiesRuthenium ComplexesSynthetic ProceduresQuímicaNew 1,2-azolylamidino complexes cis-[Ru(bipy)2(NH=C(R)az*-κ2N,N)](OTf)2 (R = Me, Ph; az∗ = pz, indz, dmpz) are synthesized via chloride abstraction after a subsequent base-catalyzed coupling of a nitrile with the previously coordinated 1,2-azole. The synthetic procedure allows the easy obtainment of complexes having different electronic and steric 1,2-azoylamidino ligands. All of the compounds have been characterized by 1H, 13C, and 15N NMR and IR spectroscopy and by monocrystal X-ray diffraction. Photophysical studies support their phosphorescence, whereas their electrochemistry reveals reversible RuII/RuIII oxidations between +1.13 and +1.25 V (vs SCE). The complexes have been successfully used as catalysts in the photooxidation of different thioethers, the complex cis-[Ru(bipy)2(NH=C(Me)dmpz-κ2N,N)]2+ showing better catalytic performance in comparison to that of [Ru(bipy)3]2+. Moreover, the significant catalytic performance of the dimethylpyrazolylamidino complex is applied to the preparation of the drug modafinil, which is obtained using ambient oxygen as an oxidant. Finally, mechanistic assays suggest that the oxidation reaction follows a photoredox route via oxygen radical anion formation.American Chemical SocietyDepartamento de Química InorgánicaFacultad de Ciencias20212021-05-17research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/704759https://dx.doi.org/10.1021/acs.inorgchem.0c03389reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7047592026-06-23T12:46:27Z |
| dc.title.none.fl_str_mv |
Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers |
| title |
Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers |
| spellingShingle |
Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers Cuéllar, Elena Catalytic Performance Chloride Abstraction Electrochemical Studies Oxidation Reactions Photocatalytic Oxidations Photophysical Studies Ruthenium Complexes Synthetic Procedures Química |
| title_short |
Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers |
| title_full |
Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers |
| title_fullStr |
Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers |
| title_full_unstemmed |
Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers |
| title_sort |
Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers |
| dc.creator.none.fl_str_mv |
Cuéllar, Elena Diez-Varga, Alberto Torroba, Tomás Domingo-Legarda, Pablo Alemán Lara, José Julián Cabrera Herranz, Silvia Martín-Alvarez, Jose M. Miguel, Daniel Villafañe, Fernando |
| author |
Cuéllar, Elena |
| author_facet |
Cuéllar, Elena Diez-Varga, Alberto Torroba, Tomás Domingo-Legarda, Pablo Alemán Lara, José Julián Cabrera Herranz, Silvia Martín-Alvarez, Jose M. Miguel, Daniel Villafañe, Fernando |
| author_role |
author |
| author2 |
Diez-Varga, Alberto Torroba, Tomás Domingo-Legarda, Pablo Alemán Lara, José Julián Cabrera Herranz, Silvia Martín-Alvarez, Jose M. Miguel, Daniel Villafañe, Fernando |
| author2_role |
author author author author author author author author |
| dc.contributor.none.fl_str_mv |
Departamento de Química Inorgánica Facultad de Ciencias |
| dc.subject.none.fl_str_mv |
Catalytic Performance Chloride Abstraction Electrochemical Studies Oxidation Reactions Photocatalytic Oxidations Photophysical Studies Ruthenium Complexes Synthetic Procedures Química |
| topic |
Catalytic Performance Chloride Abstraction Electrochemical Studies Oxidation Reactions Photocatalytic Oxidations Photophysical Studies Ruthenium Complexes Synthetic Procedures Química |
| description |
New 1,2-azolylamidino complexes cis-[Ru(bipy)2(NH=C(R)az*-κ2N,N)](OTf)2 (R = Me, Ph; az∗ = pz, indz, dmpz) are synthesized via chloride abstraction after a subsequent base-catalyzed coupling of a nitrile with the previously coordinated 1,2-azole. The synthetic procedure allows the easy obtainment of complexes having different electronic and steric 1,2-azoylamidino ligands. All of the compounds have been characterized by 1H, 13C, and 15N NMR and IR spectroscopy and by monocrystal X-ray diffraction. Photophysical studies support their phosphorescence, whereas their electrochemistry reveals reversible RuII/RuIII oxidations between +1.13 and +1.25 V (vs SCE). The complexes have been successfully used as catalysts in the photooxidation of different thioethers, the complex cis-[Ru(bipy)2(NH=C(Me)dmpz-κ2N,N)]2+ showing better catalytic performance in comparison to that of [Ru(bipy)3]2+. Moreover, the significant catalytic performance of the dimethylpyrazolylamidino complex is applied to the preparation of the drug modafinil, which is obtained using ambient oxygen as an oxidant. Finally, mechanistic assays suggest that the oxidation reaction follows a photoredox route via oxygen radical anion formation. |
| publishDate |
2021 |
| dc.date.none.fl_str_mv |
2021 2021-05-17 |
| dc.type.none.fl_str_mv |
research article http://purl.org/coar/resource_type/c_2df8fbb1 VoR http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| dc.type.openaire.fl_str_mv |
info:eu-repo/semantics/article |
| format |
article |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10486/704759 https://dx.doi.org/10.1021/acs.inorgchem.0c03389 |
| url |
http://hdl.handle.net/10486/704759 https://dx.doi.org/10.1021/acs.inorgchem.0c03389 |
| dc.language.none.fl_str_mv |
Inglés eng |
| language_invalid_str_mv |
Inglés |
| language |
eng |
| dc.rights.none.fl_str_mv |
open access http://purl.org/coar/access_right/c_abf2 |
| dc.rights.openaire.fl_str_mv |
info:eu-repo/semantics/openAccess |
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open access http://purl.org/coar/access_right/c_abf2 |
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openAccess |
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application/pdf |
| dc.publisher.none.fl_str_mv |
American Chemical Society |
| publisher.none.fl_str_mv |
American Chemical Society |
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reponame:Biblos-e Archivo. Repositorio Institucional de la UAM instname:Universidad Autónoma de Madrid |
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Universidad Autónoma de Madrid |
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Biblos-e Archivo. Repositorio Institucional de la UAM |
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Biblos-e Archivo. Repositorio Institucional de la UAM |
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15,301603 |