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, 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, Daniel
A1 Villafañe, Fernando
K1 Química inorgánica
K1 Chemistry, Inorganic
AB New 1,2-azolylamidino complexes fac-[RuCl(DMSO)3(NH[double bond, length as m-dash]C(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 precursors cis,fac-[RuCl2(DMSO)3(az*H)] (1) after subsequent base-catalyzed coupling of the appropriate nitrile 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 Royal Society of Chemistry
SN 1477-9226
YR 2023
FD 2023-11
LK http://hdl.handle.net/10259/8360
UL http://hdl.handle.net/10259/8360
LA eng
NO The authors in Valladolid gratefully acknowledge financial support from the Spanish MINECO, Spain (PGC2018-099470-B-I00), the Junta de Castilla y León (VA130618), and the Spanish Ministerio de Ciencia e Innovación (MCIN, PID2021-124691NB-I00, funded by MCIN/AEI/10.13039/501100011033/FEDER, UE). E. C. thanks the UVa for their grant. G. G.-H. gratefully acknowledges financial support from the Junta de Castilla y León, the Spanish Ministerio de Ciencia e Innovación MICIN, and the European Union Next Generation EU/PRTR (MR6NP3). A. M. A.-B. is grateful for support from the National Science Foundation CAREER grant (CHE-1652606).
DS Repositorio Institucional de la Universidad de Burgos
RD 23-nov-2024