An improved immobilised Grubbs 2 nd generation catalyst and its application in flowthrough devices, shown for on-column reaction gas chromatography (ocRGC), has been studied. The coupling of a reaction capillary and a separation column in GC/MS allows direct reaction monitoring and analysis of conversion as well as reaction kinetics. The presented permanently bonded N-heterocyclic carbene ligand shows a great stability and activity in ring closing metathesis reactions. A salt-free approach was used to generate the carbene ligand, which can be directly monitored by mass spectrometry. The very flexible design of the immobilised ligand system in reaction channels and capillaries of flow through systems allows the preparation of various catalysts using a broad variety of metal precursors. This strategy of immobilised catalytically active complexes offers a wide range of on-column reactions combinable with fast reaction screening by high throughput experimentation.
Small (≤1.4 nm) and very active Ru nanoparticles, stabilized in a polysiloxane matrix, were prepared and studied in hydrogenation reactions by the integration of catalysis and analysis. We used our strategy to combine catalytic activity and separation selectivity in a capillary microreactor, installed in a GC–MS instrument, to develop a fast and reliable screening tool for catalysis over Ru nanoparticles. A high conversion using a low catalyst loading of 0.3 mol % and temperature and long‐term stability of the catalytically active column were observed for the hydrogenation of various carbonyl compounds, which included aldehydes, ketones, and pyruvates. Additionally, we observed a high chemoselectivity for aromatic carbonyl systems. Comprehensive measurements were performed in this high‐throughput experimental setup to gain important insights into the kinetics of hydrogenation reactions at the interface between heterogeneous and homogeneous catalysis.
Characterising chemical reactions by kinetic analysis is of fundamental importance to experimentally obtain insights into reaction mechanisms. Based on such investigations reactions can be optimised and improved catalysts designed. Enhanced reaction conditions may drastically increase the performance of the reaction in terms of yield and (enantio-) selectivity. Understanding reaction kinetics in more complex systems involving adaptive chemical and dynamic systems on a molecular level as shown here is even more challenging. Here we review recent developments in monitoring reactions including the dynamic interconversion of stereoisomers by integrating (catalysed) reactions and chemical analysis in on-column reaction chromatographic devices. These recent developments allow rapid screening of reactions in great detail and are a central tool in determining reaction pathways and to understand how to control the stereodynamics of chiral molecules.
On-column reaction gas chromatography (ocRGC) was successfully utilized as high-throughput platform for monitoring of the conversion and selectivity of hydrogenation of 5-methylfurfural catalyzed by polymer-stabilized Ru and Pd nanoparticles. We were able to elucidate the effect of various reaction conditions, mainly together with the catalyst loading on the conversion rate and the selectivity of the reaction. Our strategy yields significant improvements in reaction analysis times and cost effectiveness in comparison to standard methods. We are able to demonstrate that ocRGC approach provides valuable information about the reaction system that gives scientists a tool to design suitable catalytic systems for enhanced sustainable chemistry in the future.
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