Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts

Cationic fac-[Re(CO)3(pz*H)(pypzH)]OTf (pz*H = pyrazole, pzH; 3,5-dimethylpyrazole, dmpzH; indazole, indzH; 3-(2-pyridyl)pyrazole, pypzH) were obtained from fac-[ReBr(CO)3(pypzH)] by halide abstraction with AgOTf and subsequent addition of the corresponding pyrazole. Successive deprotonation with Na...

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Autores: Merillas, Beatriz, Cuéllar, Elena, Diez Varga, Alberto, Torroba Pérez, Tomás, García Herbosa, Gabriel, Fernández, Sergio, Lloret-Fillol, Julio, Martín-Alvarez, Jose M., Miguel, Daniel, Villafañe, Fernando
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Institución:Universidad de Burgos (UBU)
Repositorio:Repositorio Institucional de la Universidad de Burgos (RIUBU)
OAI Identifier:oai:riubu.ubu.es:10259/6823
Acceso en línea:http://hdl.handle.net/10259/6823
Access Level:acceso abierto
Palabra clave:Deprotonation
Diimides
Electrodes
Ligands
Reaction mechanisms
Química inorgánica
Chemistry, Inorganic
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spelling Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction ElectrocatalystsMerillas, BeatrizCuéllar, ElenaDiez Varga, AlbertoTorroba Pérez, TomásGarcía Herbosa, GabrielFernández, SergioLloret-Fillol, JulioMartín-Alvarez, Jose M.Miguel, DanielVillafañe, FernandoDeprotonationDiimidesElectrodesLigandsReaction mechanismsQuímica inorgánicaChemistry, InorganicCationic fac-[Re(CO)3(pz*H)(pypzH)]OTf (pz*H = pyrazole, pzH; 3,5-dimethylpyrazole, dmpzH; indazole, indzH; 3-(2-pyridyl)pyrazole, pypzH) were obtained from fac-[ReBr(CO)3(pypzH)] by halide abstraction with AgOTf and subsequent addition of the corresponding pyrazole. Successive deprotonation with Na2CO3 and NaOH gave neutral fac-[Re(CO)3(pz*H)(pypz)] and anionic Na{fac-[Re(CO)3(pz*)(pypz)]} complexes, respectively. Cationic fac-[Re(CO)3(pz*H)(pypzH)]OTf, neutral complexes fac-[Re(CO)3(pz*H)(pypz)], and fac-[Re(CO)3(pypz)2Na] were subjected to photophysical and electrochemical studies. They exhibit phosphorescent decays from a prevalently 3MLCT excited state with quantum yields (Φ) in the range between 0.03 and 0.58 and long lifetimes (τ from 220 to 869 ns). The electrochemical behavior in Ar atmosphere of cationic and neutral complexes indicates that the oxidation processes assigned to ReI → ReII occurs at lower potentials for the neutral complex compared to cationic complex. The reduction processes occur at the ligands and do not depend on the charge of the complexes. The electrochemical behavior in CO2 saturated media is consistent with CO2 electrocatalyzed reduction, where the values of the catalytic activity [icat(CO2)/icat(Ar)] ranged from 2.7 to 11.5 (compared to 8.1 for fac-[Re(CO)3Cl(bipy)] studied as a reference). Controlled potential electrolysis for the pyrazole cationic (3a) and neutral (4a) complexes after 1 h affords CO in faraday yields of 61 and 89%, respectively. These values are higher for indazole complexes and may be related to the acidity of the coordinated pyrazole.Spanish MINECO, Spain (PGC2018-099470–B-I00) and Junta de Castilla y León (VA130618), and the authors in Burgos gratefully acknowledge financial support from the Junta de Castilla y León, Consejería de Educación y Cultura y Fondo Social Europeo (Project BU263P18). E.C. thanks the UVa for her grant. We also thank the ICIQ Foundation, AGAUR 2017-SGR-1647 (J.L.-F.) and the Spanish MINECO (CTQ2016-80038-R; J.L-F.), and the Spanish Ministry of Science is acknowledged for a FPU fellowship to S.F.American Chemical Society202220222020info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://hdl.handle.net/10259/6823reponame:Repositorio Institucional de la Universidad de Burgos (RIUBU)instname:Universidad de Burgos (UBU)InglésInorganic Chemistry. 2020, V. 59, n. 15, p. 11152–11165https://doi.org/10.1021/acs.inorgchem.0c01654info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-099470-B-I00info:eu-repo/grantAgreement/Junta de Castilla y León//VA130618info:eu-repo/grantAgreement/Junta de Castilla y León//BU263P18info:eu-repo/grantAgreement/AGAUR//2017-SGR-1647info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-80038-Rinfo:eu-repo/semantics/openAccessoai:riubu.ubu.es:10259/68232026-05-28T07:56:11Z
dc.title.none.fl_str_mv Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
title Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
spellingShingle Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
Merillas, Beatriz
Deprotonation
Diimides
Electrodes
Ligands
Reaction mechanisms
Química inorgánica
Chemistry, Inorganic
title_short Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
title_full Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
title_fullStr Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
title_full_unstemmed Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
title_sort Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
dc.creator.none.fl_str_mv Merillas, Beatriz
Cuéllar, Elena
Diez Varga, Alberto
Torroba Pérez, Tomás
García Herbosa, Gabriel
Fernández, Sergio
Lloret-Fillol, Julio
Martín-Alvarez, Jose M.
Miguel, Daniel
Villafañe, Fernando
author Merillas, Beatriz
author_facet Merillas, Beatriz
Cuéllar, Elena
Diez Varga, Alberto
Torroba Pérez, Tomás
García Herbosa, Gabriel
Fernández, Sergio
Lloret-Fillol, Julio
Martín-Alvarez, Jose M.
Miguel, Daniel
Villafañe, Fernando
author_role author
author2 Cuéllar, Elena
Diez Varga, Alberto
Torroba Pérez, Tomás
García Herbosa, Gabriel
Fernández, Sergio
Lloret-Fillol, Julio
Martín-Alvarez, Jose M.
Miguel, Daniel
Villafañe, Fernando
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Deprotonation
Diimides
Electrodes
Ligands
Reaction mechanisms
Química inorgánica
Chemistry, Inorganic
topic Deprotonation
Diimides
Electrodes
Ligands
Reaction mechanisms
Química inorgánica
Chemistry, Inorganic
description Cationic fac-[Re(CO)3(pz*H)(pypzH)]OTf (pz*H = pyrazole, pzH; 3,5-dimethylpyrazole, dmpzH; indazole, indzH; 3-(2-pyridyl)pyrazole, pypzH) were obtained from fac-[ReBr(CO)3(pypzH)] by halide abstraction with AgOTf and subsequent addition of the corresponding pyrazole. Successive deprotonation with Na2CO3 and NaOH gave neutral fac-[Re(CO)3(pz*H)(pypz)] and anionic Na{fac-[Re(CO)3(pz*)(pypz)]} complexes, respectively. Cationic fac-[Re(CO)3(pz*H)(pypzH)]OTf, neutral complexes fac-[Re(CO)3(pz*H)(pypz)], and fac-[Re(CO)3(pypz)2Na] were subjected to photophysical and electrochemical studies. They exhibit phosphorescent decays from a prevalently 3MLCT excited state with quantum yields (Φ) in the range between 0.03 and 0.58 and long lifetimes (τ from 220 to 869 ns). The electrochemical behavior in Ar atmosphere of cationic and neutral complexes indicates that the oxidation processes assigned to ReI → ReII occurs at lower potentials for the neutral complex compared to cationic complex. The reduction processes occur at the ligands and do not depend on the charge of the complexes. The electrochemical behavior in CO2 saturated media is consistent with CO2 electrocatalyzed reduction, where the values of the catalytic activity [icat(CO2)/icat(Ar)] ranged from 2.7 to 11.5 (compared to 8.1 for fac-[Re(CO)3Cl(bipy)] studied as a reference). Controlled potential electrolysis for the pyrazole cationic (3a) and neutral (4a) complexes after 1 h affords CO in faraday yields of 61 and 89%, respectively. These values are higher for indazole complexes and may be related to the acidity of the coordinated pyrazole.
publishDate 2020
dc.date.none.fl_str_mv 2020
2022
2022
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://hdl.handle.net/10259/6823
url http://hdl.handle.net/10259/6823
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Inorganic Chemistry. 2020, V. 59, n. 15, p. 11152–11165
https://doi.org/10.1021/acs.inorgchem.0c01654
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-099470-B-I00
info:eu-repo/grantAgreement/Junta de Castilla y León//VA130618
info:eu-repo/grantAgreement/Junta de Castilla y León//BU263P18
info:eu-repo/grantAgreement/AGAUR//2017-SGR-1647
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-80038-R
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:Repositorio Institucional de la Universidad de Burgos (RIUBU)
instname:Universidad de Burgos (UBU)
instname_str Universidad de Burgos (UBU)
reponame_str Repositorio Institucional de la Universidad de Burgos (RIUBU)
collection Repositorio Institucional de la Universidad de Burgos (RIUBU)
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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