Reaction Dynamics

Methane valorization is a promising technology to utilize this platform compound to produce aromatics and hydrocarbons. Researchers from PSI and ETH Zürich unveiled this reaction mechanism and observed the molecular growth from the ground up. Besides stepwise CH3 addition,  novel routes involving the dimerization of resonantly stabilized propargyl (C₃H₃) radicals to benzene (C₆H₆) were identified. These mechanistic insights will aid the development of valorisation strategies.

To develop sustainable lignin valorization strategies, a solid understanding of the underlying reaction mechanism is critical. By detection of highly reactive and elusive intermediates, new light could be shed on one of the most basic elementary reactions in lignin catalytic fast pyrolysis.

During the week of March 15 – 19, we had the pleasure to welcome 20 international PhD students, PostDocs and assistant professors at PSI, taking part in the first virtual HERCULES SCHOOL on Neutrons & Synchrotron Radiation.

Open shell organometallic bismuth are promising agents for catalytic applications, but difficult to characterize due to their high reactivity. The simplest methylbismuth (Bi-CH₃), a biradical species, was in-situ synthesized and spectroscopically characterized for the first time. Electronic and thermochemical properties could be obtained, which will guide future synthetic applications.

Light alkanes are abundantly available and cheap resources that are often burned at oil wells because of the missing infrastructure for valorization. Novel technologies are needed for their selective functionalization to use natural gas as an energy vector in the transition between the oil and the renewables era. Catalytic oxyhalogenation may unlock the transformation of cheap and abundant alkanes into commodities. When chlorine-based reactions are compared with bromine, improved selectivities above an iron catalyst arise from surface-confinement of the reaction mechanism in the case of chlorine as halogen.

The resonantly stabilized xylyl radicals (C₈H₉•) distinctively influence the combustion chemistry and, therefore, ultimately determine the performance of combustion engines. At that, the three different isomers (methyl group in ortho, para or meta position) exhibit notable differences at elevated temperatures. We have tracked down these dynamics on a femtosecond timescale by monitoring the response to preparation of a well-defined electronic and vibrational state.

Methylperoxy radicals are crucial oxidation intermediates and could be synthesized photolytically in an exothermic reaction. Despite their vanishingly small concentration, their temperature could be measured after a few ten thousand collisions inside the reactor, which opens up the possibility of time-resolved operando temperature measurements. Also the reaction energy to yield methyl cations and oxygen could be determined with sub-kJ mol^–1 precision, which firmly anchors the methylperoxy energetics to that of well-known stable species and opens up the possibility of highly accurate radical thermochemistry measurements.

Studying organic molecular magnets is a challenge, because the high-spin diradical character of these compounds dramatically increases the reactivity and reduces the lifetime. Researchers from PSI, ETH Zurich, Wollongong and Melbourne, Australia succeeded in taming the meta-xylylene diradical and were able to study its electronic and thermochemical properties.