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
K1 Química
K1 Electrolysis
K1 Photocatalysts
K1 1,2-azolylamidino complexes
K1 Electrólisis
K1 Fotocatalizadores
K1 Complejos de 1,2-azolilamidino
K1 2210.05 Electroquímica
AB New 1,2-azolylamidino complexes fac-[RuCl(DMSO)3(NHvC(R)az*-κ2N,N)]OTf [R = Me (2), Ph (3); az* =pz (pyrazolyl, a), indz (indazolyl, b)] are synthesized via chloride abstraction from their corresponding pre-cursors 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 1 H NMR, 13 CNMR 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 electro-chemical behavior in CO2 media is consistent with CO2 electrocatalytic reduction. The catalytic activityexpressed as [icat (CO 2)/ip (Ar)] ranged from 1.7 to 3.7 for the 1,2-azolylamidino complexes at voltages ofca. −2.7 to −3 V vs. ferrocene/ferrocenium. Controlled potential electrolysis showed rapid decompositionof the Ru catalysts. Photocatalytic CO 2 reduction experiments using compounds 1b, 2b and 3b carriedout 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 traceamounts of formate. The combined turnover number for the production of formate and CO is ca. 100after 8 h and follows the order 1b < 2b ≈ 3b.
PB Royal Society of Chemistry
SN 1477-9226
YR 2023
FD 2023
LK https://uvadoc.uva.es/handle/10324/67687
UL https://uvadoc.uva.es/handle/10324/67687
LA eng
NO Dalton Transactions, 2023, vol. 52, issue 45, p.16974–16983
NO Producción Científica
DS UVaDOC
RD 22-jun-2024