RT Journal Article
T1 Exploring Protonation Sites with Cation-Responsive Polyethylene glycol (PEG) Tethers in [FeFe]-Hydrogenase Mimics
A1 Torres Ruiz, Alejandro
A1 Aguado Rivero, Sergio
A1 Collado Martínez, Alba
A1 Sáez, Elena
A1 Gómez Gallego, María Del Mar
A1 Sierra Rodríguez, Miguel Ángel
AB imics of [FeFe]-hydrogenases having two [(μ-adt)Fe2(CO)6] moieties linked through 1,2,3-triazole rings with polyethylene glycol (PEG) chains [(–OCH2CH2O–)4 (7) and (–OCH2CH2O–)5 (8)] are able to coordinate to alkali ions (Na+, K+) via the O-PEG atoms and the triazole-N3 positions. Electrocatalytic studies in trifluoroacetic acid (TFA) demonstrate that their catalytic performance is affected by the presence of Na+ and K+ salts. The addition of NaPF6 decreases the electrocatalytic activity of 7 and 8 (about 50% reduction of the TOF values). As, in TFA, 7 and 8 could be protonated in both the triazole and adt-amino groups, the reduction in TOF values suggests that NaPF6 inhibits the contribution of the triazolium species to the electrocatalytic process, likely due to the involvement of the triazole-N3 positions in Na+ binding. However, the addition of KPF6 either does not change (7) or increases the TOF values (8). 1H NMR titration experiments demonstrate that, despite the presence of K+ ions in the media, triazolium salts are formed. Therefore, the TOF values should reflect the contribution of species protonated in both the triazole and adt-amino groups to the HER process.
PB Royal Society of Chemistry
YR 2025
FD 2025-01-17
LK https://hdl.handle.net/20.500.14352/124054
UL https://hdl.handle.net/20.500.14352/124054
LA eng
NO Torres, Alejandro, et al. «Exploring Protonation Sites with Cation-Responsive Polyethylene Glycol (PEG) Tethers in [FeFe]-Hydrogenase Mimics». Inorganic Chemistry Frontiers, vol. 12, n.o 14, 2025, pp. 4480-93
NO Ministerio de Ciencia, Innovación y Universidades (España)
DS Docta Complutense
RD 23 ene 2026