Manganese photocatalysts enabled versatile room-temperature C-H arylation reactions by means of continuous visible-light photoflow, thus allowing for efficient C-H arylations in 30 minutes with ample scope. The robustness of the manganese-catalyzed photoflow strategy was shown by visible light-induced gram-scale synthesis, clearly outperforming the batch performance.

A ruthenium‐catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes has been established, enabling the preparation of various bridgehead N‐fused [5,6]‐bicyclic heteroarenes through regioselective electrochemical C−H/N−H annulation without chemical metal oxidants. Novel azaruthenabicyclo[3.2.0]heptadienes were fully characterized and identified as key intermediates. Mechanistic studies are suggestive of an oxidatively induced reductive elimination pathway within a ruthenium(II/III) regime.

Asymmetric ruthenium-catalyzed C–H alkylations were enabled by a chiral C2-symmetric carboxylic acid. The mild cooperative ruthenium­(II) catalysis set the stage for the assembly of chiral tetrahydrocarbazoles and cyclohepta­[b]­indoles with high levels of enantioselectivity at room temperature. Mechanistic studies by experiment and computation identified a fast C–H ruthenation, along with a rate- and enantio-determining proto-demetalation. The asymmetric induction was governed by weak attractive secondary dispersion interactions as found in NCI analysis of the key transition states.

A series of [(PMP)Rh(CO)Cl] complexes was synthesised and the impact of the metalloligands Cu, Li and Zn on the CO stretching band was analysed.