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 González, Elena
A1 Diez Varga, Alberto
A1 Torroba, Tomás
A1 Domingo Legarda, Pablo
A1 Alemán Lara, José Julián
A1 Cabrera, Silvia
A1 Martín Álvarez, José Miguel
A1 Miguel San José, Daniel
A1 Villafañe González, Fernando
K1 Ketones
K1 Cetonas
K1 Oxidation
K1 Oxidación
K1 Nitrogen compounds
K1 Compuestos nitrogenados
K1 Ligands
K1 Ligandos
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 ACS Publications
SN 1520-510X
YR 2021
FD 2021
LK https://uvadoc.uva.es/handle/10324/53363
UL https://uvadoc.uva.es/handle/10324/53363
LA eng
NO Inorganic Chemistry, 2021, vol. 60, n. 10. p. 7008–7022
NO Producción Científica
DS UVaDOC
RD 17-jul-2024