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.
Palladium on metal oxides and on activated carbon with particular properties (high palladium dispersion, low degree of reduction, water content) are shown to be highly active (tunrover number, TON = 20,000; turnover frequency, TOF = 16,600), selective and robust catalysts for Suzuki cross-couplings of aryl bromides and activated aryl chlorides. Catalysts and reaction protocol offer combined advantages of high catalytic efficiency under ambient conditions (air and moisture), easy separation and reuse and quantitative recovery of palladium. The palladium concentration in solution during the reaction correlates clearly with the progress of the reaction and indicates that dissolved molecular palladium is in fact the catalytically active species. Dissolved palladium is redeposited onto the support at the end of the reaction. Additional minimization of the palladium content in solution (down to 0.1 ppm) could be achieved by simple procedures which meet the requirements of pharmaceutical industry.
The review reports the general approach, problems, potential and recent advances in heterogeneously catalyzed Heck reactions. It demonstrates the advantages and limitations for practical applications at present. A literature overview is given separately for substrates that are easier to activate (aryl iodides, activated aryl bromides) and for non-/deactivated aryl bromides and aryl chlorides during the period between 2001 and 2005. New approaches and strategies for the activation of aryl bromides and especially chlorides by heterogeneous catalysts are discussed. The argumentations clearly exceed simple separation and reuse arguments. Particular attention is given to the relation between homogeneous and heterogeneous catalysis from the mechanistic point of view. Very recent reports show clear success in the understanding of corresponding reaction mechanisms. Palladium species dissolved from the support are proven to be responsible for high activity and selectivity in Heck reactions by supported catalysts (Pd on activated carbon, oxides, polymers and in zeolites). The careful choice of optimum catalyst and reaction conditions are crucial and allowed the development of simple heterogeneous catalysts that activate even deactivated aryl chlorides with high yields within few hours of reaction time.
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