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Herein, we describe the investigation of electrochemical bromination of electron-rich arenes in a 200% cell. For this application, at first, the influence of an excess of supporting electrolyte (Bu 4 NBr) on chemical bromination was investigated. The application of >4.0 equiv of Bu 4 NBr proved to enhance the regioselectivity of the bromination process for O- and N-substituted arenes considerably. The linear paired electrolysis was then optimized upon these insights, and a number of electron-rich arenes could be brominated in high yields with excellent regioselectivity. The use of O 2 as a sacrificial starting material in combination with 2-ethylanthraquinone as a catalyst leads to the enhanced formation of H 2 O 2 at the cathode, resulting in current efficiencies >150% for a considerable number of examples.

The synthesis of unsymmetrical diorganyl selanes was accomplished under electrochemical conditions in an undivided cell utilizing a magnesium cathode and a carbon anode made out of aryl and alkyl iodides and diselanes. This electrochemical cross-electrophile coupling (eXEC) was accomplished using a simple nickel catalyst formed in situ out of Ni(acac) 2 and 2,2'-bipyridine in DMF at ambient temperatures. The reaction showed good functional group compatibility, and heteroaryl iodides, such as thiophene or pyridine derivatives, were well accepted.

Herein, we describe the application of a flow system for the generation of a soluble organo sodium compound and the transformation of this primary nucleophile with various Weinreb amides for the synthesis of alkyl-aryl ketones. Thereafter, the generation of secondary sodium intermediates, such as benzylic sodium nucleophiles or ortho -metalated sodium nucleophiles from various carbon pre-nucleophiles, is described. These transformations generated more complex ketones, and in this investigation the key aspect was to identify factors for the chemoselective and regioselective C-H deprotonation of concurring sites within the starting material. Finally, the direct synthesis of ketones from carboxylic acids and the organo sodium compound is described, revealing interesting aspects regarding the nucleophilicity and basicity of the alkyl sodium reagent.

The role of the inorganic substrate termination, within the organic-inorganic interface, has been well studied for systems that contain strong localised bonding. However, how varying the substrate termination affects coordination to delocalised electronic states, like that found in aromatic molecules, is an open question. Azupyrene, a non-alternant polycyclic aromatic hydrocarbon, is known to bind strongly to metal surfaces through its delocalised π orbitals, thus yielding an ideal probe into delocalised surface-adsorbate interactions. Normal incidence X-ray standing wave (NIXSW) measurements and density functional theory calculations are reported for the adsorption of azupyrene on the (111), (110) and (100) surface facets of copper to investigate the dependence of the adsorption structure on the substrate termination. Structural models based on hybrid density functional theory calculations with non-local many-body dispersion yield excellent agreement with the experimental NIXSW results. No statistically significant difference in the azupyrene adsorption height was observed between the (111) and (100) surfaces. On the Cu(110) surface, the molecule was found to adsorb 0.06 ± 0.04 Å closer to the substrate than on the other surface facets. The most energetically favoured adsorption site on each surface, as determined by DFT, is subtly different, but in each case involved a configuration where the aromatic rings were centred above a hollow site, consistent with previous reports for the adsorption of small aromatic molecules on metal surfaces.