Reduction of N<sub>2</sub>O with hydrosilanes catalysed by RuSNS nanoparticles

“…N 2 O is a chemically stable and kinetically inert molecule [16], its deoxygenation reaction remains difficult, as even thermal decomposition is limited by a high kinetic barrier despite being thermodynamically favorable [14, 17, 18]. According to the previous reports, most of the degradation of N 2 O relied on metal catalysts, such as Mn, Fe, Co, Ni, Cu, Bi, Ru, Re [19–32]. However, those metals exist obvious weaknesses more or less, such as the complicated ligand preparation process, the harsh reaction conditions, rare and expensive, or the low selectivity from the abundant metals [33, 34].…”

Section: Introductionmentioning

confidence: 99%

Deoxygenation reactions of nitrous oxide assisted by oriented external electric field

Zhang,

Li,

Lei

et al. 2024

Int J of Quantum Chemistry

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Due largely to the high stability and the potential ozone‐depleting, the transformation of greenhouse gas nitrous oxide has gained much attentions. In present paper, a new insight into the deoxygenation of nitrous oxide with silane was reported by using oriented external electric field (OEEF) as a catalytic strategy. When the OEEF was employed, the reaction barrier of deoxygenation was marvelously decreased as it was oriented along the positive NO/OSi bond‐axis. Especially the field strength is 300 × 10−4 a.u., the differences are up to 22.4/18.3 kcal mol−1 as compared with that of nonfield. In addition, once the H atom in SiH4 was replaced by methyl, two reaction modes were obtained, in which the deoxygenation process was easier when the N2O captured the H atom attached to the Si atom, not attached to the C atom. Further, the solvent effects of deoxygenation reaction were also considered, but with a weak influence were obtained.

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“…Anthropogenic N 2 O, mainly produced from the use of nitrogen-containing fertilizers, biomass and fossil fuel combustion, and industrial chemical processes, such as adipic and nitric acid syntheses, has been claimed as the main source for the upward trend in its atmospheric concentration in the last decades . Therefore, strategies developed to mitigate its concentration, either by lowering its emissions or by implementing processes that can degrade it to chemical species with low environmental impact, are drawing increased attention …”

Section: Introductionmentioning

confidence: 99%

Catalytic Nitrous Oxide Reduction with H₂ Mediated by Pincer Ir Complexes

et al. 2022

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Reduction of nitrous oxide (N2O) with H2 to N2 and water is an attractive process for the decomposition of this greenhouse gas to environmentally benign species. Herein, a series of iridium complexes based on proton-responsive pincer ligands (1–4) are shown to catalyze the hydrogenation of N2O under mild conditions (2 bar H2/N2O (1:1), 30 °C). Among the tested catalysts, the Ir complex 4, based on a lutidine-derived CNP pincer ligand having nonequivalent phosphine and N-heterocyclic carbene (NHC) side donors, gave rise to the highest catalytic activity (turnover frequency (TOF) = 11.9 h–1 at 30 °C, and 16.4 h–1 at 55 °C). Insights into the reaction mechanism with 4 have been obtained through NMR spectroscopy. Thus, reaction of 4 with N2O in tetrahydrofuran-d 8 (THF-d 8) initially produces deprotonated (at the NHC arm) species 5 NHC , which readily reacts with H2 to regenerate the trihydride complex 4. However, prolonged exposure of 4 to N2O for 6 h yields the dinitrogen Ir(I) complex 7 P , having a deprotonated (at the P-arm) pincer ligand. Complex 7 P is a poor catalytic precursor in the N2O hydrogenation, pointing out to the formation of 7 P as a catalyst deactivation pathway. Moreover, when the reaction of 4 with N2O is carried out in wet THF-d 8, formation of a new species, which has been assigned to the hydroxo species 8, is observed. Finally, taking into account the experimental results, density functional theory (DFT) calculations were performed to get information on the catalytic cycle steps. Calculations are in agreement with 4 as the TOF-determining intermediate (TDI) and the transfer of an apical hydrido ligand to the terminal nitrogen atom of N2O as the TOF-determining transition state (TDTS), with very similar reaction rates for the mechanisms involving either the NHC– or the P–CH2 pincer methylene linkers.

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Reduction of N₂O with hydrosilanes catalysed by RuSNS nanoparticles

Abstract: A series of RuSNS nanoparticles, prepared by decomposition of Ru(COD)(COT) with H2 in the presence of a SNS ligand, has been found to catalyse the reduction of the greenhouse gas...

Cited by 6 publications

References 48 publications

Ruthenium nanoparticles stabilized by 1,2,3-triazolylidene ligands in the hydrogen isotope exchange of E–H bonds (E = B, Si, Ge, Sn) using deuterium gas

Ruthenium nanoparticles stabilized by 1,2,3-triazolylidene ligands in the hydrogen isotope exchange of E–H bonds (E = B, Si, Ge, Sn) using deuterium gas

Deoxygenation reactions of nitrous oxide assisted by oriented external electric field

Catalytic Nitrous Oxide Reduction with H₂ Mediated by Pincer Ir Complexes

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Reduction of N2O with hydrosilanes catalysed by RuSNS nanoparticles

Abstract: A series of RuSNS nanoparticles, prepared by decomposition of Ru(COD)(COT) with H2 in the presence of a SNS ligand, has been found to catalyse the reduction of the greenhouse gas...

Cited by 6 publications

References 48 publications

Ruthenium nanoparticles stabilized by 1,2,3-triazolylidene ligands in the hydrogen isotope exchange of E–H bonds (E = B, Si, Ge, Sn) using deuterium gas

Ruthenium nanoparticles stabilized by 1,2,3-triazolylidene ligands in the hydrogen isotope exchange of E–H bonds (E = B, Si, Ge, Sn) using deuterium gas

Deoxygenation reactions of nitrous oxide assisted by oriented external electric field

Catalytic Nitrous Oxide Reduction with H2 Mediated by Pincer Ir Complexes

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Reduction of N₂O with hydrosilanes catalysed by RuSNS nanoparticles

Catalytic Nitrous Oxide Reduction with H₂ Mediated by Pincer Ir Complexes