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A variety of palladium on activated carbon catalysts differing in Pd dispersion, Pd distribution, Pd oxidation state, and water content were tested in Heck reactions of aryl bromides with olefins. The optimization of the catalyst (structure ± activity relationship) and reaction conditions (temperature, solvent, base, and Pd loading) allowed Pd/C catalysts with very high activity for Heck reactions of unactivated bromobenzene (turnover number (TON) % 18 000, turnover frequency (TOF) up to 9000, Pd concentrations down to 0.005 mol %) to be developed. High Pd dispersion, low degree of reduction, sufficient content of water, and uniform Pd impregnation are criteria for the most active system. The catalysts combine high activity and selectivity under ambient conditions (air and moisture), easy separation (filtration), and quantitative recovery of palladium. De-termination of Pd in solution after and during the reaction, and catalyst characterization before and after the reaction (transmission electron microscopy (TEM), X-ray diffraction (XRD)), indicate dissolution/reprecipitation of palladium during the reaction. The Pd concentration in solution is highest at the beginning of the reaction and is a minimum (< 1 ppm) at the end of the reaction. Palladium leaching correlates significantly with the reaction parameters.

The plasma potential of 13.56-MHz low-pressure argon glow discharges has been measured for various modes of applying the rf power in a geometrically asymmetric planar system. The plasma potential is determined from the energy distribution of positive ions incident on the grounded electrode. The voltages on the excitation electrode (target electrode) are carefully measured and the capacitive sheath approximation is used to relate these measured voltages to the measured plasma potential. This approximation is successful in most of the situations encountered in this low-pressure (20 mTorr) relatively low-power density regime. The effects of superimposing dc voltages on the excitation electrode are discussed.

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The Forum Article critically summarizes investigations and discussions on the nature and role of potential active species in C-C coupling reactions of the Heck type using catalyst systems with "ligand-free" inorganic salts, simple inorganic complexes, and supported and nonsupported (colloidal) Pd particles. From a series of experiments and reports, it can be concluded that the "active species" is generated in situ in catalytic systems at higher temperature conditions (>100 degrees C). In all heterogeneous systems with solid Pd catalysts, Pd is dissolved from the solid catalyst surface under reaction conditions by a chemical reaction (complex formation and/or oxidative addition of the aryl halide), forming extremely active coordinatively unsaturated Pd species. Pd is partially or completely redeposited onto the support at the end of the reaction when the aryl halide is used up. The Pd dissolution-redeposition processes correlate with the reaction rate and are strongly influenced by the reaction conditions. Skilled preparation of the catalyst and careful adjustment of the reaction conditions allowed the development of highly active heterogeneous catalysts (Pd/C, Pd/metal oxide, and Pd/zeolite), converting aryl bromides and aryl chlorides in high yields and short reaction times. Reaction conditions have been developed allowing the conversion of bromobenzene with turnover numbers (TONs) of 10(7) and even of unreactive aryl chlorides (chlorobenzene and chlorotoluene) in high yields with simple "ligand-free" Pd catalyst systems like PdCl2 or Pd(OH)2 in the absence of any organic ligand. Simple coordinatively unsaturated anionic palladium halide (in particular, bromo) complexes [PdXn](m-) play a crucial role as precursor and active species in all ligand-free and heterogeneous catalyst systems and possibly in Heck reactions at all.

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