2026-04-28T06:12:43Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/68152022-08-24T00:05:45Zcom_10259_4354com_10259_5086com_10259_2604col_10259_4355

Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers Cuéllar, Elena Diez Varga, Alberto Torroba Pérez, Tomás Domingo-Legarda, Pablo Alemán, José Cabrera, Silvia Martín-Alvarez, Jose M. Miguel, Daniel Villafañe, Fernando Ketones Ligands Materials Nitrogen compounds Oxidation 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. 2022-08-23T10:29:35Z 2022-08-23T10:29:35Z 2022-08-23T10:29:35Z 2021-05 info:eu-repo/semantics/article 0020-1669 http://hdl.handle.net/10259/6815 10.1021/acs.inorgchem.0c03389 1520-510X eng Inorganic Chemistry. 2021, V. 60, n. 10, p. 7008–7022 https://doi.org/10.1021/acs.inorgchem.0c03389 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-099470-B-I00/ES/APLICACION DE MOLECULAS NANOGRAFENICAS EN LA MEJORA DE LAS PROPIEDADES OPTOLELECTRONICAS DE CELULAS SOLARES ORGANICAS info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-095038-B-I00/ES/CONTROLANDO PROCESOS ORGANOCATALITICOS Y FOTOCATALITICOS ASIMETRICOS PARA LA SINTESIS DE MOLECULAS ORGANICAS info:eu-repo/grantAgreement/Junta de Castilla y León//VA130618 info:eu-repo/grantAgreement/Junta de Castilla y León//BU263P18 http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess Atribución 4.0 Internacional American Chemical Society