Automation and microfluidic tools potentially enable efficient, fast, and focused reaction development of complex chemistries, while minimizing resource- and material consumption. The introduction of automation-assisted workflows will contribute to the more sustainable development and scale-up of new and improved catalytic technologies. Herein, the application of automation and microfluidics to the development of a complex asymmetric hydrogenation reaction is described. Screening and optimization experiments were performed using an automated microfluidic platform, which enabled a drastic reduction in the material consumption compared to conventional laboratory practices. A suitable catalytic system was identified from a library of Ru^II-diamino precatalysts. In situ precatalyst activation was studied with ¹H/³¹P nuclear magnetic resonance (NMR), and the reaction was scaled up to multigram quantities in a batch autoclave. These reactions were monitored using an automated liquid-phase sampling system. Ultimately, in less than a week of total experimental time, multigram quantities of the target enantiopure alcohol product were provided by this automation-assisted approach.

Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.

Any catalyst should be efficient and stable to be implemented in practice. This requirement is particularly valid for manganese hydrogenation catalysts. While representing a more sustainable alternative to conventional noble metal-based systems, manganese hydrogenation catalysts are prone to degrade under catalytic conditions once operation temperatures are high. Herein, we report a highly efficient Mn(I)-CNP pre-catalyst which gives rise to the excellent productivity (TOF° up to 41 000 h⁻¹) and stability (TON up to 200 000) in hydrogenation catalysis. This system enables near-quantitative hydrogenation of ketones, imines, aldehydes and formate esters at the catalyst loadings as low as 5–200 p.p.m. Our analysis points to the crucial role of the catalyst activation step for the catalytic performance and stability of the system. While conventional activation employing alkoxide bases can ultimately provide catalytically competent species under hydrogen atmosphere, activation of Mn(I) pre-catalyst with hydride donor promoters, e.g. KHBEt₃, dramatically improves catalytic performance of the system and eliminates induction times associated with slow catalyst activation.

Aromatization of furan and substituted furans over zeolite catalysts is a promising reaction to convert cellulose-derived compounds into valuable aromatic hydrocarbons and light olefins. A lack of understanding of the reaction mechanism however hinders further development of this process. Here, we propose the reaction mechanism, underlying the chemistry of furan and methanol co-aromatization over HZSM-5 zeolite catalyst. Applying ¹³C isotope labeling in a combination with NMR spectroscopy and high temporal resolution gas chromatography-mass spectrometry analysis, we demonstrate that aromatization of furan and methanol are not mechanistically separated and can be described within the dual-cycle hydrocarbon pool mechanism. Cofeeding furan with methanol leads to a significant enhancement of light aromatics selectivity and increased catalyst lifetime.

Catalytic reductions of carbonyl-containing compounds are highly important for the safe, sustainable, and economical production of alcohols. Herein, we report on the efficient transfer hydrogenation of ketones catalyzed by a highly potent Mn(I)−NHC complex. Mn−NHC 1 is practical at metal concentrations as low as 75 ppm, thus approaching loadings more conventionally reserved for noble metal based systems. With these low Mn concentrations, catalyst deactivation is found to be highly temperature dependent and becomes especially prominent at increased reaction temperature. Ultimately, understanding of deactivation pathways could help close the activity/stability-gap with Ru and Ir catalysts towards the practical implementation of sustainable earth-abundant Mn-complexes.

Every measurement technique operates on a given timescale and measurements using emissive small molecule sensors are no exception. A family of luminescent sensors providing first optical characterization of dynamic phenomena in polymers at a timescale of several microseconds is described. This performance originates from the dynamics manifested in the excited state of the sensor molecules where diffusioncontrolled events select the emission color while radiative phenomena define the global operation timescale. Since the mechanism responsible for signal generation is confined to the short lived excited state of emissive probe, it is possible observe an unprecedented link between the timescale of sensory action and that of photoluminescence. An application of this new methodology is demonstrated by performing general, short timescale detection of glass transitions in a temperature ranges precluding the informative range of conventional techniques by tens of degrees.

Catalytic hydrogenation and dehydrogenation reactions form the core of the modern chemical industry. This vast class of reactions is found in any part of chemical synthesis starting from the milligram-scale exploratory organic chemistry to the multi-ton base chemicals production. Noble metal catalysis has long been the key driving force in enabling these transformations with carbonyl substrates and their nitrogen-containing counterparts. This review is aimed at introducing the reader to the remarkable progress made in the last three years in the development of base metal catalysts for hydrogenations and dehydrogenative transformations.

The reaction mechanism of ester hydrogenation catalyzed by a bidentate aminophosphine ligated manganese catalyst was studied by DFT calculations. Particular emphasize was placed on the role of the alkoxide base additives. The presence of such basic promoters as KO^tBu can improve the catalyst activity by lowering the activation barriers of H₂ dissociation as well as the hydrogenation step. The promoting effect of KO^tBu on H₂ activation is much stronger than that of tert-butoxides with other alkali metals, which is crucial for the catalyst regeneration from the deactivated Mn-alkoxide species in the resting state.

Structural heterogeneity defines the properties of many functional polymers and it is often crucial for their performance and ability to withstand mechanical impact. Such heterogeneity, however, poses a tremendous challenge for characterization of these materials and limits our ability to design them rationally. Herein we present a practical methodology capable of resolving the complex mechanical behavior and tracking mechanical impact in discrete phases of segmented polyurethane—a typical example of a structurally complex polymer. Using direct optical imaging of photoluminescence produced by a small-molecule organometallic mechano-responsive sensor we observe in real time how polymer phases dissipate energy, restructure, and breakdown upon mechanical impact. Owing to its simplicity and robustness, this method has potential in describing the evolution of complex soft-matter systems for which global characterization techniques fall short of providing molecular-level insight.

Metal-ligand cooperative properties of a bis-N-heterocyclic carbene ruthenium CNC pincer catalyst and its activity in CO₂ hydrogenation to formates were studied by DFT calculations complemented by NMR spectroscopy and kinetic measurements. The dearomatized Ru-CNC∗ pincer (1∗) is significantly more reactive toward metal-ligand cooperative activation of H₂ and CO₂ than the structurally related phosphine-based Ru-PNP complex. The enhanced reactivity of Ru-CNC∗ stems from the combination of electronic properties of this system and the reduced geometric constraints imposed onto the Ru center by the large and flexible CNC chelate. Heterolytic dissociation of H₂ by 1∗ results in the bis-hydrido complex 2 that is active in hydrogenation of CO₂. However, under commonly applied reaction conditions, the catalyst rapidly deactivates via metal-ligand cooperative paths. The transient formation of the dearomatized complex Ru-CNC∗ (1∗) in the course of the reaction leads to the irreversible cooperative activation of CO₂, resulting in the stable adduct 3 that is not catalytically competent. By an increase in the H₂/CO₂ ratio, this deactivation path can be effectively suppressed, resulting in a stable and rather high catalytic performance of Ru-CNC. (Chemical Equation Presented).

The catalytic reduction of carboxylic acid derivatives has witnessed a rapid development in recent years. These reactions, involving molecular hydrogen as the reducing agent, can be promoted by heterogeneous and homogeneous catalysts. The milestone achievements and recent results by both approaches are discussed in this Review. In particular, we focus on the mechanistic aspects of the catalytic hydrogenation and highlight the bifunctional nature of the mechanism that is preferred for supported metal catalysts as well as homogeneous transition metal complexes.

The reaction mechanism of CO₂hydrogenation by pyridine-based Ru-PNP catalyst in the presence of DBU base promoter was studied by means of density functional theory calculations. Three alternative reaction channels promoted by the complexes potentially present under the reaction conditions, namely the dearomatized complex 2 and the products of cooperative CO₂(3) and H₂(4) addition, were analysed. It is shown that the bis-hydrido Ru-PNP complex 4 provides the unique lowest-energy reaction path involving a direct effectively barrierless hydrogenolysis of the polarized complex 5∗. The reaction rate in this case is controlled by the CO₂activation by Ru-H that proceeds with a very low barrier of ca. 20 kJ mol^-1. The catalytic reaction can be hampered by the formation of a stable formato-complex 5. In this case, the rate is controlled by the H₂insertion into the Ru-OCHO coordination bond, for which a barrier of 65 kJ mol^-1is predicted. The DFT calculations suggest that the preference for the particular route can be controlled by varying the partial pressure of H₂in the reaction mixture. Under H₂-rich conditions, the former more facile catalytic path should be preferred. Dedicated kinetic experiments verify these theoretical predictions. The apparent activation energies measured at different H₂/CO₂molar ratios are in a perfect agreement with the calculated values. Ru-PNP is a highly active CO₂hydrogenation catalyst allowing reaching turnover frequencies in the order of 10⁶h^-1at elevated temperatures. Moreover, a minor temperature dependency of the reaction rate attainable in excess H₂points to the possibility of efficient CO₂hydrogenation at near-ambient temperatures. This journal is

Interaction of hydrogen with model Cu-Zn methanol synthesis catalyst prepared by decomposition of mixed hydroxicarbonate is studied by inelastic neutron scattering, in situ FTIR/MS, and thermal analysis. Reduced (Cu _0.08,Zn_0.92)O mixed oxide accumulates 6H/Cu, mainly as hydride, hydroxyl and formate species. The reduction of copper in the (Cu,Zn)O mixed oxide occurs via a reversible redox interaction with H₂ and absorption of protons as OH^--groups with ν = 3250 cm^-1 and δ ≈ 1430-1480 cm^-1. Kinetic and thermodynamic parameters of this process are evaluated. The weight loss during the reduction is due to the decomposition of the residual carbonate groups to CO₂ via formate intermediates, which occurs in the presence of hydrogen. Exposure of (Cu,Zn)O to air prior to the reduction strongly affects the kinetic parameters of the reduction process.