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Ruthenium nanoparticles (NPs) immobilized on an amine‐functionalized polymer‐grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full hydrogenation of benzofuran and quinoline derivatives is achieved under pure H2, introducing CO2 into the H2 gas phase leads to an effective shutdown of the arene hydrogenation while preserving the activity for the hydrogenation of the heteroaromatic part. The selectivity switch originates from the generation of ammonium formate species on the surface of the materials by catalytic hydrogenation of CO2. The CO2 hydrogenation is fully reversible, resulting in a robust and rapid switch between the two states of the catalyst adapting its performance in response to the feed gas composition. A variety of benzofuran and quinoline derivatives were hydrogenated to fully or partially saturated products in high selectivity and yields simply by altering the composition of the feed gas from H2 to H2/CO2. The adaptive catalytic system thus provides controlled access to valuable products using a single catalyst rather than two specific and distinct catalysts with static reactivity. [ABSTRACT FROM AUTHOR]

The rapidly growing importance of green hydrogen and renewable carbon resources as essential feedstocks for sustainable chemical value chains opens room for disruptive innovations regarding chemical production processes. The fluctuation and variability associated with non‐fossil energy and raw material supply holds many challenges for catalysts to cope with the resulting dynamics. However, many new opportunities also arise once catalyst design starts to aim at performance that is "adaptive" rather than "task‐specific". In this Scientific Perspective, we propose to define adaptivity in catalysis on the basis of three essential properties that are reversibility, rapidity, and robustness (R3 rule). Promising design strategies and selected examples are described to substantiate the scientific concept and to highlight its potential for chemical energy conversion. [ABSTRACT FROM AUTHOR]

Copper chromite is decorated with iron carbide nanoparticles, producing a magnetically activatable multifunctional catalytic system. This system (ICNPs@Cu2Cr2O5) can reduce aromatic ketones to aromatic alcohols when exposed to magnetic induction. Under magnetic excitation, the ICNPs generate locally confined hot spots, selectively activating the Cu2Cr2O5 surface while the global temperature remains low (≈80 °C). The catalyst selectively hydrogenates a scope of benzylic and non‐benzylic ketones under mild conditions (3 bar H2, heptane), while ICNPs@Cu2Cr2O5 or Cu2Cr2O5 are inactive when the same global temperature is adjusted by conventional heating. A flow reactor is presented that allows the use of magnetic induction for continuous‐flow hydrogenation at elevated pressure. The excellent catalytic properties of ICNPs@Cu2Cr2O5 for the hydrogenation of biomass‐derived furfuralacetone are conserved for at least 17 h on stream, demonstrating for the first time the application of a magnetically heated catalyst to a continuously operated hydrogenation reaction in the liquid phase. [ABSTRACT FROM AUTHOR]

The electrocatalytic transformation of carbon dioxide has been a topic of interest in the field of CO2 utilization for a long time. Recently, the area has seen increasing dynamics as an alternative strategy to catalytic hydrogenation for CO2 reduction. While many studies focus on the direct electron transfer to the CO2 molecule at the electrode material, molecular transition metal complexes in solution offer the possibility to act as catalysts for the electron transfer. C1 compounds such as carbon monoxide, formate, and methanol are often targeted as the main products, but more elaborate transformations are also possible within the coordination sphere of the metal center. This perspective article will cover selected examples to illustrate and categorize the currently favored mechanisms for the electrochemically induced transformation of CO2 promoted by homogeneous transition metal complexes. The insights will be corroborated with the concepts and elementary steps of organometallic catalysis to derive potential strategies to broaden the molecular diversity of possible products. [ABSTRACT FROM AUTHOR]

The catalytic reduction of carbon dioxide (CO2) is considered a major pillar of future sustainable energy systems and chemical industries based on renewable energy and raw materials. Typically, catalysts and catalytic systems are transforming CO2 preferentially or even exclusively to one of the possible reduction levels and are then optimized for this specific product. Here, we report a cobalt‐based catalytic system that enables the adaptive and highly selective transformation of carbon dioxide individually to either the formic acid, the formaldehyde, or the methanol level, demonstrating the possibility of molecular control over the desired product platform. [ABSTRACT FROM AUTHOR]

Highly selective β‐methylation of alcohols was achieved using an earth‐abundant first row transition metal in the air stable molecular manganese complex [Mn(CO)2Br[HN(C2H4PiPr2)2]] 1 ([HN(C2H4PiPr2)2]=MACHO‐iPr). The reaction requires only low loadings of 1 (0.5 mol %), methanolate as base and MeOH as methylation reagent as well as solvent. Various alcohols were β‐methylated with very good selectivity (>99 %) and excellent yield (up to 94 %). Biomass derived aliphatic alcohols and diols were also selectively methylated on the β‐position, opening a pathway to "biohybrid" molecules constructed entirely from non‐fossil carbon. Mechanistic studies indicate that the reaction proceeds through a borrowing hydrogen pathway involving metal–ligand cooperation at the Mn‐pincer complex. This transformation provides a convenient, economical, and environmentally benign pathway for the selective C−C bond formation with potential applications for the preparation of advanced biofuels, fine chemicals, and biologically active molecules [ABSTRACT FROM AUTHOR]

This article, published in Angewandte Chemie International Edition, discusses the development of an adaptive catalyst for the selective hydrogenation of bicyclic heteroaromatics. The catalyst, based on amine-functionalized ruthenium nanoparticles, can switch its selectivity in product formation by controlling the composition of the feedgas. This selectivity switch is reversible, rapid, and robust, and is attributed to the formation and decomposition of ammonium formate species. The research, conducted by Alexis Bordet, Walter Leitner, and their colleagues, provides valuable insights into the design of catalysts for hydrogenation reactions. [Extracted from the article]

The novel [Ru(Acriphos)(PPh3)(Cl)(PhCO2)] [ 1; Acriphos=4,5-bis(diphenylphosphino)acridine] is an excellent precatalyst for the hydrogenation of CO2 to give formic acid in dimethyl sulfoxide (DMSO) and DMSO/H2O without the need for amine bases as co-reagents. Turnover numbers (TONs) of up to 4200 and turn over frequencies (TOFs) of up to 260 h−1 were achieved, thus rendering 1 one of the most active catalysts for CO2 hydrogenations under additive-free conditions reported to date. The thermodynamic stabilization of the reaction product by the reaction medium, through hydrogen bonds between formic acid and clusters of solvent or water, were rationalized by DFT calculations. The relatively low final concentration of formic acid obtained experimentally under catalytic conditions (0.33 mol L−1) was shown to be limited by product-dependent catalyst inhibition rather than thermodynamic limits, and could be overcome by addition of small amounts of acetate buffer, thus leading to a maximum concentration of free formic acid of 1.27 mol L−1, which corresponds to optimized values of TON=16×103 and TOFavg≈103 h−1. [ABSTRACT FROM AUTHOR]

Transparent films were prepared by cross-linking polyunsaturated poly(ether carbonate)s obtained by the multicomponent polymerization of CO2, propylene oxide, maleic anhydride, and allyl glycidyl ether. Poly(ether carbonate)s with ABXBA multiblock structures were obtained by sequential addition of mixtures of propylene oxide/maleic anhydride and propylene oxide/allyl glycidyl ether during the polymerization. The simultaneous addition of both monomer mixtures provided poly(ether carbonate)s with AXA triblock structures. Both types of polyunsaturated poly(ether carbonate)s are characterized by diverse functional groups, that is, terminal hydroxy groups, maleate moieties along the polymer backbone, and pendant allyl groups that allow for versatile polymer chemistry. The combination of double bonds substituted with electron-acceptor and electron-donor groups enables particularly facile UV- or redox-initiated free-radical curing. The resulting materials are transparent and highly interesting for coating applications. [ABSTRACT FROM AUTHOR]

The development of a tailored tridentate ligand enabled the synthesis of a molecular ruthenium-triphos catalyst, eliminating dimerization as the major deactivation pathway. The novel catalyst design showed strongly increased performance and facilitated the hydrogenation of highly challenging lactam substrates with unprecedented activity and selectivity. [ABSTRACT FROM AUTHOR]