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Verfasst von:Bogado, André Luiz [VerfasserIn]   i
 Paschai Darian, Leon K. [VerfasserIn]   i
 Bürgy, David [VerfasserIn]   i
 dos Santos, Lucas da Silva [VerfasserIn]   i
 Ueno, Leonardo Tsuyoshi [VerfasserIn]   i
Titel:Hydrogen production by the Ruthenium(II) complex bearing a bulky PNP ligand
Titelzusatz:a catalyst for the decomposition of formic acid and/or ammonium formate
Verf.angabe:André L. Bogado, Leon Kambiz Paschai Darian, David Bürgy, Lucas da Silva dos Santos, and Leonardo Tsuyoshi Ueno
E-Jahr:2024
Jahr:24 December 2024
Umfang:8 S.
Illustrationen:Illustrationen
Fussnoten:Online veröffentlicht: 11. Dezember 2024 ; Gesehen am 13.03.2025
Titel Quelle:Enthalten in: ACS omega
Ort Quelle:Washington, DC : ACS Publications, 2016
Jahr Quelle:2024
Band/Heft Quelle:9(2024), 51 vom: Dez., Seite 50758-50765
ISSN Quelle:2470-1343
Abstract:The five-coordinate complex [RuCl2(PNP)] (1) was synthesized from the binuclear [RuCl2(p-cym)]2 with a PNP-type ligand (PNP = 3,6-di-tert-butyl-1,8-bis(diisopropylphosphino)methyl)-9H-carbazole - (CbzdiphosiPr)H) in a toluene solution, within 20 h at 110 °C, producing a green solid, which was precipitated with a 1/1 mixture of n- pentane/HMDSO. The complex was characterized by NMR─1H, 13C, and 31P{1H}, mass spectroscopy─LIFDI, FTIR, UV/vis spectroscopy, and cyclic voltammetry, as well as a description of the optimized structure by DFT calculation. The reactivity of 1 was investigated in the presence of potassium triethylborohydride (KBEt3H, in THF solution of 1.0 mol L-1) and ammonium formate (NH4HCO2), producing an in situ hydride complex and a formate intermediate species coordinated to the ruthenium center. The complex 1, loaded with 0.08%, catalyzed the decomposition of ammonium formate (AF) into H2, CO2, and NH3 in THF solutions at 80 °C, with 94% of H2 and TOF = 206 h-1 (molar ratio [Ru]/AF = 1/1204). The catalytic activity increased remarkably for the decomposition of formic acid (FA) as a substrate to produce H2 and CO2. In the HMDSO solution at 80 °C, a conversion of 100% was obtained in relation to H2 and TOF = 3010 h-1 (molar ration [Ru]/FA/NEt3 = 1/1204/843). In an equimolar mixture of AF/FA in HMDSO solution at 80 °C, without additives, the complex 1 catalyzed the decomposition of both with 100% of H2 and TOF = 987 h-1 (molar ratio [Ru]/AF/FA= 1/602/602). Under the later conditions, as well as upon AF decomposition, carbamic acid [HO(C═O)NH2] was obtained as a coproduct of a secondary reaction between NH3 and CO2 (yield = 50% in relation to the amount of AF). A kinetic study for decomposing FA, in the range of 60-100 °C, provided ΔS‡ = −9.7 e.u, ΔG‡ = 13.35 kJ mol-1, and Ea = 64 kJ mol-1, suggesting that the mechanism is more associative than for the known complexes.
DOI:doi:10.1021/acsomega.4c09025
URL:Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.

kostenfrei: Volltext: https://doi.org/10.1021/acsomega.4c09025
 DOI: https://doi.org/10.1021/acsomega.4c09025
Datenträger:Online-Ressource
Sprache:eng
K10plus-PPN:1919718818
Verknüpfungen:→ Zeitschrift

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