RT info:eu-repo/semantics/article
T1 1,2-Azolylamidino ruthenium(ii) complexes with DMSO ligands: electro- and photocatalysts for CO2 reduction
A1 Jennings, Murphy
A1 Cuéllar González, Elena
A1 Rojo, Ariadna
A1 Ferrero, Sergio
A1 García-Herbosa, Gabriel
A1 Nganga, John
A1 Angeles Boza, Alfredo M
A1 Martín Alvarez, Jose M
A1 Miguel San José, Daniel
A1 Villafañe González, Fernando
A1 Cuéllar, Elena
A1 Angeles-Boza, Alfredo M.
A1 Martín-Alvarez, Jose M.
A1 Miguel, Daniel
A1 Villafañe, Fernando
K1 Química
K1 Electro- and photocatalysts
K1 CO2 reduction
K1 23 Química
AB New 1,2-azolylamidino complexes fac-[RuCl(DMSO)3(NHvC(R)az*-κ2 N,N)]OTf [R = Me (2), Ph (3); az* =pz (pyrazolyl, a), indz (indazolyl, b)] are synthesized via chloride abstraction from their corresponding precursors cis,fac-[RuCl2(DMSO)3(az*H)] (1) after subsequent base-catalyzed coupling of the appropriatenitrile with the 1,2-azole previously coordinated. All the compounds are characterized by 1H NMR, 13C NMR and IR spectroscopy. Those derived from MeCN are also characterized by X-ray diffraction. Electrochemical studies showed several reduction waves in the range of −1.5 to −3 V. The electrochemical behavior in CO2 media is consistent with CO2 electrocatalytic reduction. The catalytic activity expressed as [icat(CO2)/ip(Ar)] ranged from 1.7 to 3.7 for the 1,2-azolylamidino complexes at voltages of ca. −2.7 to −3 V vs. ferrocene/ferrocenium. Controlled potential electrolysis showed rapid decomposition of the Ru catalysts. Photocatalytic CO2 reduction experiments using compounds 1b, 2b and 3b carried out in a CO2-saturated MeCN/TEOA (4 : 1 v/v) solution containing a mixture of the catalyst and [Ru (bipy)3] 2+ as the photosensitizer under continuous irradiation (light intensity of 150 mW cm−2 at 25 °C, λ >300 nm) show that compounds 1b, 2b and 3b allowed CO2 reduction catalysis, producing CO and trace amounts of formate. The combined turnover number for the production of formate and CO is ca. 100 after 8 h and follows the order 1b < 2b ≈ 3b.
PB RCS
SN 1477-9234
YR 2024
FD 2024
LK https://uvadoc.uva.es/handle/10324/67697
UL https://uvadoc.uva.es/handle/10324/67697
LA spa
NO Dalton Transactions, Noviembre 2023, n. 52
NO Producción Científica
DS UVaDOC
RD 23-jun-2024