2026-04-18T20:04:25Zhttps://riubu.ubu.es/oai/requestoai:riubu.ubu.es:10259/68232022-08-31T00:05:23Zcom_10259_4354com_10259_5086com_10259_2604com_10259_4363col_10259_4355col_10259_4364
Repositorio Institucional de la Universidad de Burgos
author
Merillas, Beatriz
author
Cuéllar, Elena
author
Diez Varga, Alberto
author
Torroba Pérez, Tomás
author
García Herbosa, Gabriel
author
Fernández, Sergio
author
Lloret-Fillol, Julio
author
Martín-Alvarez, Jose M.
author
Miguel, Daniel
author
Villafañe, Fernando
2022-08-30T11:31:00Z
2022-08-30T11:31:00Z
2020-07
0020-1669
http://hdl.handle.net/10259/6823
10.1021/acs.inorgchem.0c01654
1520-510X
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.
eng
Deprotonation
Diimides
Electrodes
Ligands
Reaction mechanisms
Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts
info:eu-repo/semantics/article
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