Speeding up borylation Catalytic is the rare reaction that can selectively target stronger over weaker saturated carbon–hydrogen (C–H) bonds. However, trade-off has been slow and requires high excess of hydrocarbon. Oeschger et al. now report right ligand (2-methylphenanthroline) coordinated to iridium accelerate by 50- 80-fold. This rate enhancement enables selective primary C–H bonds with hydrocarbon as limiting reagent. The also unusually for β-C–H in heterocycles. Science , this issue p. 736

Reversible catalytic reactions operate under thermodynamic control, and thus, establishing a selective system poses considerable challenge. Herein, we report reversible transfer hydrocyanation protocol that exhibits high selectivity for the thermodynamically less favorable branched isomer. Selectivity is achieved by exploiting lower barrier C–CN oxidative addition reductive elimination at benzylic positions in absence of cocatalytic Lewis acid. Through design novel type HCN donor, practical,...

The development of efficient catalysts for the hydrogenation CO

Hydrogenation of CO2 to methanol is foreseen as a key step close the carbon cycle. In this study, we show that introducing Ga into silica-supported nanoparticles based on group 8-9 transition noble metals (M = Ru, Os, Rh, and Ir - MGa@SiO2) switches their reactivity from producing mostly methane (sel. > 97%) (>50% CH3OH/DME sel.) alongside CO only byproduct. These catalysts, prepared via surface organometallic chemistry (SOMC) approach, consist small, alloyed, narrowly distributed MGa...

The olefin metathesis activity of silica-supported molybdenum oxides depends strongly on metal loading and preparation conditions, indicating that the nature and/or amounts active sites vary across compositionally similar catalysts. This is illustrated by comparing Mo-based (pre)catalysts prepared impregnation (2.5-15.6 wt % Mo) a model material (2.3 synthesized via surface organometallic chemistry (SOMC). Analyses FTIR, UV-vis, Mo K-edge X-ray absorption spectra show these are composed...

The synthesis of well-defined materials as model systems for catalysis and related fields is an important pillar in the understanding catalytic processes at a molecular level. Various approaches employing organometallic precursors have been developed established to make monodispersed supported nanoparticles, nanocrystals, films. Using rational design principles, new family based on group 10 metals suitable generation small nanoparticles metal oxides has developed. Particle formation SiO2...

The direct conversion of syngas to ethanol is a promising route for the sustainable production value-added chemicals and fuels. While Fe-promoted Rh-based catalysts have long been studied because their notable activity selectivity towards ethanol, nature Rh-Fe interaction catalyst structure under reaction conditions remain poorly understood due intrinsic complexity heterogeneous prepared by conventional approaches. In this work, we construct well-defined RhFe@SiO2 model via surface...

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...

N-heterocyclic carbenes (NHCs) have emerged as versatile ligands in organometallic chemistry, prized for their strong σ-donating and tunable electronic properties. They stabilize diverse motifs, well clusters, nanoparticles, particularly those based on the coin-age metals—Cu, Ag, Au. Importantly, carbene 13C NMR isotropic chemical shift (δiso) of NHC-coinage metal complexes varies significantly across these elements, reflecting nuanced interplay structural factors. Here, we investigate...

The direct conversion of syngas to ethanol is a promising route for the sustainable production value-added chemicals and fuels. While Fe-promoted Rh-based catalysts have long been studied because their notable activity selectivity towards ethanol, nature Rh-Fe interaction catalyst structure under reaction conditions remain poorly understood due complexity heterogeneous prepared by conventional approaches. In this work, we construct well-defined RhFe@SiO2 model via surface organometallic...

The direct conversion of syngas to ethanol is a promising route for the sustainable production value-added chemicals and fuels. While Fe-promoted Rh-based catalysts have long been studied because their notable activity selectivity toward ethanol, catalyst structure nature Rh-Fe interaction remain poorly understood under reaction conditions, due intrinsic complexity heterogeneous prepared by conventional approaches. In this work, we construct well-defined RhFe@SiO2 model via surface...

N-heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry, prized for their strong σ-donating and tunable electronic properties. They used to stabilize a wide range of motifs, including clusters nanoparticles, based particular on coinage metals—Cu, Ag, Au. Notably, the carbene 13C NMR isotropic chemical shift (δiso) NHC-coinage metal complexes varies significantly across these elements, reflecting nuanced interplay structural factors. Here, we study carbon NHC-Au(I)-X...

N-Heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry, prized for their strong σ-donating and tunable electronic properties. They used to stabilize a wide range of motifs, including clusters nanoparticles, based particular on coinage metals─Cu, Ag, Au. Notably, the carbene 13C NMR isotropic chemical shift (δiso) NHC-coinage metal complexes varies significantly across these elements, reflecting nuanced interplay structural factors. Here, we study carbon NHC-Au(I)-X...

Carbon dioxide is a major contributor to global climate change and ocean acidification, making efficient capture utilization required step for sustainable development. A pivotal aspect of development close the carbon cycle by converting CO2 with “green” H2 value-added product or fuel, such as methanol. In this context, supported metal catalysts have been extensively investigated, focusing on role promoters and/or supports drive catalytic performance. particular, besides classical like zinc,...

Rh-based catalysts modified by transition metals have been intensively studied for CO2 hydrogenation due to their high activity. However, understanding the role of promoters at molecular level remains challenging ill-defined structure heterogeneous catalysts. Here, we constructed well-defined RhMn@SiO2 and Rh@SiO2 model via surface organometallic chemistry combined with thermolytic precursor (SOMC/TMP) approach rationalize promotional effect Mn in hydrogenation. We show that addition shifts...

The development of efficient catalysts for the hydrogenation CO2 to methanol using “green” H2 is foreseen be a key step close carbon cycle. In this study, we show that small and narrowly distributed alloyed PtGa nanoparticles supported on silica, prepared via surface organometallic chemistry (SOMC) approach, display notable activity methanol, reaching 7.2 mol h-1 molPt-1 formation rate with 54% intrinsic CH3OH selectivity. This reactivity sharply contrasts what expected Pt, which favors...

Peroxide compounds are used both in laboratory and industrial processes for the electrophilic epoxidation of olefins. Using NMR-spectroscopy, we investigate why certain peroxides engage this type reaction while others require activation by metal catalysts, e.g. methyltrioxorhenium (MTO). More precisely, an analysis 17O NMR chemical shift quadrupolar coupling parameters provides insights into relative energy specific frontier molecular orbitals relevant reactivity. For organic or H2O2 a large...

The development of efficient catalysts for the hydrogenation CO2 to methanol using “green” H2 is foreseen be a key step close carbon cycle. In this study, we show that small and narrowly distributed alloyed PtGa nanoparticles supported on silica, prepared via surface organometallic chemistry (SOMC) approach, display notable activity methanol, reaching 7.2 mol h-1 molPt-1 formation rate with 54% intrinsic CH3OH selectivity. This reactivity sharply contrasts what expected Pt, which favors...

The development of efficient catalysts for the hydrogenation CO2 to methanol is foreseen as a key step close carbon cycle and enable sustainable development. In this study, we show that introducing Ga into silica-supported nanoparticles based on group 8-9 noble transition metals (M = Ru, Os, Rh, Ir – MGa@SiO2), switches their reactivity from producing purely CH4 (selectivity >97%) (50% CH3OH/DME) alongside CO only byproduct. These catalysts, prepared via surface organometallic chemistry...

<p><i>Typically, reversible catalytic reactions operate under thermodynamic control and thus establishing a selective system poses considerable challenge. In this manuscript, we report yet kinetically transfer hydrocyanation protocol. Selectivity is achieved by exploiting the lower barrier for C–CN oxidative addition reductive elimination at benzylic positions in absence of co-catalytic Lewis acid. The design novel type HCN donor was crucial to realizing practical,...

The catalytic activity of silica-supported molybdenum oxides for olefin metathesis depends strongly on the metal loading and preparation conditions indicating that nature and/or amounts active sites vary across catalysts. This is illustrated by comparing Mo-based (pre)catalysts prepared impregnation with different loadings (2.5-15.6 wt% Mo) a well-defined model material (2.3 via surface organometallic chemistry (SOMC) synthetic approach. Analyses FTIR, UV-vis, Mo K-edge X-ray absorption...

The synthesis of well-defined materials as model systems for catalysis and related fields is an important pillar in the understanding catalytic processes at a molecular level. Various approaches employing organometallic precursors have been developed established to make monodispersed supported nanoparticles, nanocrystals, films. Using rational design principles, new family based on group 10 metals suitable generation small nanoparticles metal oxides has developed. Particle formation SiO2...

The direct conversion of syngas to ethanol is a promising route for the sustainable production value-added chemicals and fuels. While Fe-promoted Rh-based catalysts have long been studied because their notable activity selectivity towards ethanol, nature Rh-Fe interaction catalyst structure under reaction conditions remain poorly understood due complexity heterogeneous prepared by conventional approaches. In this work, we construct well-defined RhFe@SiO2 model via surface organometallic...

Supported catalysts are central to industrial catalytic processes. While traditional synthesis methods often yield poorly defined materials, thus complicating structural elucidation, Surface Organometallic Chemistry (SOMC) offers a solution, producing well-defined structures. Recent advances in SOMC precursor development have shown that amidinate-based precursors privileged class of generate supported metallic nanoparticles. In context, this study investigates the grafting mechanism...

Hydrogenation of CO2 to methanol is foreseen as a key step close the carbon cycle and enable sustainable development. In this study, we show that introducing Ga into silica-supported nanoparticles based on group 8-9 transition noble metals (M = Ru, Os, Rh, Ir – MGa@SiO2) switches their reactivity from producing methane (sel. >97%) (50% CH3OH/DME sel.) alongside CO only byproduct. These catalysts, prepared via surface organometallic chemistry approach, consist small, alloyed narrowly...