RT info:eu-repo/semantics/article
T1 Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers
A1 Cuéllar, Elena
A1 Diez Varga, Alberto
A1 Torroba Pérez, Tomás
A1 Domingo-Legarda, Pablo
A1 Alemán, José
A1 Cabrera, Silvia
A1 Martín-Alvarez, Jose M.
A1 Miguel, Daniel
A1 Villafañe, Fernando
K1 Ketones
K1 Ligands
K1 Materials
K1 Nitrogen compounds
K1 Oxidation
K1 Química inorgánica
K1 Chemistry, Inorganic
AB 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.
PB American Chemical Society
SN 0020-1669
YR 2021
FD 2021-05
LK http://hdl.handle.net/10259/6815
UL http://hdl.handle.net/10259/6815
LA eng
NO The authors in Valladolid gratefully acknowledge financial support from the Spanish MINECO of Spain (PGC2018099470-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. The authors in Universidad Autónoma de Madrid acknowledge financial support from the Spanish MINECO (RTI2018-095038-B-I00). We also thank Gabriel García-Herbosa and Irene Abajo-Cuadrado (Universidad de Burgos, Burgos, Spain) for helping us with the electrochemical and photophysical experiments, respectively.
DS Repositorio Institucional de la Universidad de Burgos
RD 20-abr-2024