Palladium® complexes aqueous catalysis

I 6 Heterogeneous Asymmetric Catalysis in Aqueous Media Table 6.1 Asymmetric allylic alkylation in water with a chiral polymeric palladium complex. 

C—C Coupling Reactions. This field of aqueous organometallic catalysis is dominated by the use of palladium complexes with sulfonated phosphine ligands however, iV-heterocyclic carbene complexes have also appeared on the scene (196,197). Most of the synthetic procedures were developed on a laboratory scale, where recycling of the catalyst was not a top priority. Therefore, many of the reactions were carried out in homogeneous solutions, either in water or in... 

Water is so extensively used in catalytic oxidation reactions that usually this fact is regarded as a natural feature and remains unnoticed. Wacker oxidation of olefins by palladium complexes involves water as a nucleophilic reagent, and thus the whole Wacker-type chemistry, which has developed into a powerful and versatile method of organic synthesis, is derived from aqueous catalysis [178]. The role of the nature of the co-oxidant and the mechanism of deactivation of the palladium catalyst due to aggregation and growth of inactive metal particles were recently investigated, and such study may have relevance for other processes catalyzed by phosphine-less palladium catalysts [179]. 

Pt(S2CNMe(Hex))2] and [Pd(S2CNMe(Hex))2] have been synthesized and used as precursors to grow the first TOPO-capped PtS and PdS nanoparticles and thin films of PtS and PdS by the metallo-organic chemical vapor deposition (MOCVD) method [204]. Platinum and palladium chalcogenides find applications in catalysis [205-210] and materials science [211,212]. The synthesis of thiocarbamato complexes of platinum and palladium from reaction of an aqueous solution of ammonium dithiocarbamate with the platinum or palladium salt has been reported by Nakamoto et al. [213]. However... 

The previous examples involve reduction (hydrogenation) of organic molecules, but transition metal complexes can also catalyze oxidation. For example, the Wacker process, which has been widely used to convert ethylene to acetaldehyde, depends on catalysis by palladium(II) in the presence of copper(II) in aqueous HC1. The role of the copper chloride is to provide a means of using air to reoxidize the palladium to palladium(II). Once again, Zeise-type coordination of the ethylene to the metal center is believed to be involved ... 

Homogeneous catalysis by redox metals is also known for nonelectro-chemical processes. Thus, ethylene is oxidized to acetaldehyde in the Wacker process in aqueous solutions containing Pd " (504). Apart from complex formation and insertion (505), ionic oxidation and reduction may take place. It is noteworthy that palladium oxidation to form ions that act as homogeneous catalysts has been suggested as an important step in ethylene electrooxidation on solid palladium electrocatalysts 28, 29). 

SAPC can perform a broad spectrum of reactions such as hydroformylation, hydrogenation and oxidation, for the synthesis of bulk and fine chemicals, pharmaceuticals and their intermediates. Rhodium complexes are the most extensively used, but complexes of ruthenium, platinum, palladium, cobalt, molybdenum and copper have also been employed [63-65]. Owing to interfacial reactions, one of the main advantages of SAPC upon biphasic catalysis is that the solubility of the reactant in the catalytic aqueous-phase does not limit the performance of the supported aqueous phase catalysts. 

Reviews on palladium(n) chemistry include one on the formation of its polyamine complexes in aqueous solution.190 A volume of reviews on organopalladium chemistry puts special emphasis on the catalysis of C-C bond forming processes known as the Heck reaction.191... 

Likholobov et al. [42] have followed up on the original report by Zudin et al. [8] and proposed the following catalytic cycle for Ph3P-complexed palladium WGSR catalysis system run in 20% aqueous trifluoroacetic acid. 

Oxidation of terminal olefins to methyl ketones by aqueous palladium chloride and oxygen is very slow, but addition of micellar sodium lauryl sulphate increases the rate of formation of 2-octanone from 1-octene twentyfold at 50 °C. There is weaker catalysis by the non-ionic surfactant Brij-35 and inhibition by cationic surfactants. " Oxidation of diosphenol (35) in basic aqueous tetradecyltrimethylammonium chloride is faster and more effective than in water, giving a higher yield of (36). Two attempts at effecting the enantioselective reduction of aromatic ketones, one in micelles of R-dodecyl-dimethyl-a-phenylethylammonium bromide and the other in sodium cho-late micelles, both give optical yields of less than 2%. Rather more success was obtained in the catalysed oxidation of L-Dopa, 3,4-dihydroxyphenyI-alanine. In the presence of the Cu complex of N-lauroyl-L-histidine in cetyl-trimethylammonium bromide micelles reaction was 1.42 (pH 6.90, 30 °C) to... 

The process of choice for acetaldehyde production is ethylene oxidation according to the so-called Wacker-Hoechst process [route (c) in Topic 5.3.2]. The reaction proceeds by homogeneous catalysis in an aqueous solution of HQ in the presence of palladium and copper chloride complexes. The oxidation of ethylene occurs in a stoichiometric reaction of PdQ2 with ethylene and water that affords acetaldehyde, metallic palladium (oxidation state 0), and HQ [step (a) in Scheme 5.3.5). The elemental Pd is reoxidized in the process by Cu(II) chloride that converts in this step into Cu(I) chloride [step (b) in Scheme 5.3.5). The Cu(II) chloride is regenerated by oxidation with air to finally close the catalytic cycle [step (c) in Scheme 5.3.5). 

It should be noted that cross-coupling in the presence of phosphine complexes of palladium usually requires high amounts of catalyst, with initial loadings of 25-30 mol% not being uncommon. An entirely new approach to the Suzuki reaction is phosphine-free palladium catalysis. The use of palladium catalysts without the addition of phosphine ligands for cross-coupling with organoboron compounds in aqueous media opened a new chapter in the story of this powerful synthetic method. This approach allows catalyst efficiency to be dramatically increased, and the reaction to be performed under milder conditions. 

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