Site-Selective and Late-Stage Deuteration of (Hetero)arenes with Supported Iridium Nanoparticles

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2822 - 2826

Published: Jan. 31, 2025

Deuterated compounds have emerged as critical tools across diverse research areas, including pharmaceuticals, where deuterium incorporation can modulate the absorption, distribution, metabolism, and excretion (ADME) properties of drugs. In this study, we report development a new hydrogen/deuterium (H/D) exchange catalyst based on supported iridium nanoparticles that enables selective deuteration arenes heteroarenes under mild conditions. Using C6D6 source, our catalytic system achieves high chemo- regioselectivity, avoiding common side reactions such hydrogenation dehalogenation observed with traditional heterogeneous catalysts. Notably, occurs selectively at para- meta-C(sp2)–H bonds, leaving ortho-C(sp2)–H C(sp3)–H bonds intact, exhibits broad functional group tolerance, ketones, amides, alkenes, aryl ethers, acidic protons. The nature was confirmed via filtration mercury drop tests. This work presents for regioselective complex molecules, offering complementary site selectivity to existing homogeneous methods possibility being used in late-stage pharmaceuticals.

Language: Английский

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Catalytic Photothermal Hydrogenation of Carbon Dioxide to Liquid Fuels using Pt/GaN Prepared via Surface Organometallic Chemistry

ChemSusChem, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Renewable liquid fuels are expected to play a crucial role in transitioning more sustainable future. Their synthesis via the hydrogenation of CO2 using solar energy emerges as promising technology, that combines both use renewable primary source and (re)utilization major greenhouse gas. In this context, GaN has attracted lot attention harnessing drive chemical transformations. work we study by 1H solid-state NMR spectroscopy, revealing presence terminal Ga-OH, bridging Ga-NH-Ga well Ga-OH-Ga surface functional groups combinations thereof. With knowledge hand, make organometallic chemistry (SOMC) prepare Pt/GaN catalyst with highly dispersed Pt nanoparticles on GaN. Under photothermal conditions visible light (>320 nm), synthesized promotes C2+ products such acetone, EtOH, iPrOH, acetic acid batch reactor at 60 °C 1 bar pressure, while pristine counterpart only produces minor amounts MeOH acetone. Furthermore, recycling test was performed showcase stability over multiple reaction cycles.

Language: Английский

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Surface gallium hydride on Ga2O3 polymorphs: a comparative solid-state NMR study

Chinese Journal of Structural Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 100561 - 100561

Published: Feb. 1, 2025

Language: Английский

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Alloyed molybdenum enables efficient alcohol hydrodeoxygenation with supported bimetallic catalysts

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Bimetallic heterogeneous catalysts combining group 9 metals (Rh, Ir) or 10 (Ni, Pd, Pt) with Mo on a silica-based support have been synthesized via surface organometallic chemistry and assessed in their catalytic activity for the hydrodeoxygenation (HDO) of alcohols particular emphasis structural evolution role Mo. The investigation was conducted an air-free approach to isolate any sample alterations exclusively those caused by reaction. Structural analysis performed using combination (S)TEM, IR, XAS. It found that Ir-Mo/SiO2, Rh-Mo/SiO2, Pt-Mo/SiO2 display high primary, secondary, tertiary alcohol deoxygenation, while Pd-Mo/SiO2 selectively catalyses deoxygenation. Other combinations as well corresponding monometallic materials do not same activity. X-ray absorption spectroscopy confirmed metallic states M (M = Ni, Rh, Ir, Pt), K-edge XANES showed varying amounts Mo(0), Mo(iv) Mo(vi) depending metal counterpart fresh materials, indicated complete conversion lower oxidation (IV 0) during For Pt, alloy formation (M-Mo) identified M-Mo paths EXAFS supported CO-IR spectroscopy. In contrast where some Mo(0) is present at nanoparticle surface, Pd-Mo forms but likely retains core, suggested CO-chemisorption. Reactivity studies suggest primarily undergo dehydration-hydrogenation, evidenced olefin MoO x /SiO2, Ir/SiO2 Ir-Mo/SiO2 under inert conditions. contrast, primary secondary follow different mechanism, correlated presence species highlighting C-O bond activation. These findings provide new insights into structure-activity relationships Mo-based bimetallic catalysts, underscoring influence strong substrate dependence mechanistic pathways.

Language: Английский

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Switching the product selectivity from methane to methanol in CO2 hydrogenation via Cu-modified vacancy engineering at MoS2 edge sites

Journal of Energy Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

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