Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers
EntityUAM. Departamento de Química Inorgánica
PublisherAmerican Chemical Society
10.1021/acs.inorgchem.0c03389Inorganic Chemistry. 60.10 (2021): 7008-7022
ISSN0020-1669 (print); 1520-510X (online)
ProjectGobierno de España. PGC2018-099470-B-I00; Gobierno de España. RTI2018-095038-B-I00
SubjectsCatalytic Performance; Chloride Abstraction; Electrochemical Studies; Oxidation Reactions; Photocatalytic Oxidations; Photophysical Studies; Ruthenium Complexes; Synthetic Procedures; Química
Rights© 2021 American Chemical Society
Esta obra está bajo una Licencia Creative Commons Atribución 4.0 Internacional.
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.
Google Scholar: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
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