The use of molten tetraalkylammonium and phosphonium halide salts as an alternative reaction medium allows to run Heck reactions without additive phosphine ligands in high yields.

Redox flow batteries based on aqueous electrolytes with organic active material (ORFB) have great potential for the development of environmentally safe and ecologically sustainable energy storage systems. To be competitive with the state-of-the-art vanadium redox flow battery, organic electrolytes must meet a whole range of requirements. We investigated different anthraquinone-based electrolytes, i.e. anthraquinone-2,6-disulfonic acid, anthraquinone-2,7-disulfonic acid (2,7-AQDS), anthraquinone-2-sulfonic acid, and 1,2-dihydroxybenzene-3,5-disulfonic acid (BQDS) with respect to their solubility in sulfuric acid, their electrical conductivity, and their viscosity. For this purpose, the influence of the concentration of sulfuric acid and the active species on the electrolyte properties was determined. Using NMR spectroscopy we analysed the thermal and electrochemical stability of 2,7-AQDS and BQDS electrolytes. The electrochemical stability was also monitored by cyclic voltammetry. Both methods have also indicated the absence of crossover phenomena. Furthermore, the influence of the electrolyte properties on the performance of the ORFB was investigated. Comparison with the vanadium electrolyte allowed us to estimate these kinds of requirements in order to develop a comparable all-organic flow battery.

The synthetic potential of stereoselective, palladium-catalyzed hydro(het)arylation reactions of bi-, tri- and tetracyclic (hetero)alkenes in the presence of phospines and arsines as highly efficient ligands was studied. The mechanism of this reductive Heck reaction becomes more complex in the case of benzonorbornenes. Hydroarylation of diazabicyclo-[2.2.1]heptenes provides a stereoselective access to aryldiaminocyclopentanes. Electron-deficient arylpalladium complexes shift the reaction towards the product of a formal 1,2-hydrazidoarylation reaction of 1,3-cyclopentadiene by a stereoselective C-N cleavage. Due to steric reasons, rigid bicyclo[2.2.2]octenes react slower in hydroarylation reactions than the corresponding bicyclo[2.2.1]heptenes. The more flexible bicyclo[4.2.2]decene system already tends to undergo domino-Heck reactions, even under reductive conditions. When a tetracyclic cis-allylcyclopropane is carbopalladated in the presence of formates, the neighboring cyclopropane ring is attacked in the first reported example of a π,σ domino-Heck reaction.

The syntheses and photochemical properties of the novel aminoaryldiarylboranes, 4, which are isoelectronic with triarylmethane dyes, and also pyrrolyl- 8, and indolyl-diarylboranes 11, are described. The fluorescence spectra are strongly dependent on the solvent. The use of o-disubstituted arenes as stabilizing substituents at the boron atom leads to highly coloured solids which are stable to air and moisture. The structures of the triarylboranes 4a and b were confirmed by X-ray analyses.