Palladium immobilization

Kobayashi, J. and Mori, Y. and Kobayashi, S. (2005). Triphase Hydrogenation Reaetions Utilizing Palladium-Immobilized Capillaiy Column Reaetors and a Demonstration of Suitability for Large Scale Synthesis. Adv. Synth. Catal, 347, 1889-1892. 

The carbonylation of aryl halides was performed with [diiodobis(3-methyl-2(3H)-benzothiazolylidene)palladium] immobilized in tetrabutylammonium bromide (melt), [G4GiIm]BF4, [G4CiIm]Cl, [G4CiIm]Br, and tricaprylmethyl-ammonium chloride (aliquat). Palladium acetate associated with phosphines immobilized in [C4GiIm][PF6] or [G4CiIm]BF4 catalyze hydroxycarbonylation of aryl halides and benzyl chloride derivatives (Scheme 19), and the acids are separated by extraction with water. ... 

This review will consist of three parts (i) rationale and need for immobilizing palladium on a solid support, (ii) comparison of various palladium immobilization systems and (iii) applications of these solid-bound palladium catalysts in organic chemistry. Some personal speculations about the future of this burgeoning field will also be included for the sole purpose of eliciting further interest and discussion. The term solid support will be... 

Glos and Reiser [23] introduced aza-bis(oxazolines) as new chiral ligands for copper and palladium catalysts. Because of the structural flexibility of these compounds they also prepared an immobilized ligand by covalent grafting to methoxypoly(ethyleneglycol) (structures 14 and 15 in Scheme 9). 

Chitosan (Fig. 27) was deposited on sihca by precipitation. The palladium complex was shown to promote the enantioselective hydrogenation of ketones [80] with the results being highly dependent on the structure of the substrate. In the case of aromatic ketones, both yield and enantioselectiv-ity depend on the N/Pd molar ratio. Low palladium contents favored enan-tioselectivity but reduced the yield. Very high conversions were obtained with aliphatic ketones, although with modest enantioselectivities. More recently, the immobilized chitosan-Co complex was described as a catalyst for the enantioselective hydration of 1-octene [81]. Under optimal conditions, namely Co content 0.5 mmolg and 1-octene/Co molar ratio of 50, a 98% yield and 98% ee were obtained and the catalyst was reused five times without loss of activity or enantioselectivity. 

The observed distribution can be readily explained upon assuming that the only part of polymer framework accessible to the metal precursor was the layer of swollen polymer beneath the pore surface. UCP 118 was meta-lated with a solution of [Pd(AcO)2] in THF/water (2/1) and palladium(II) was subsequently reduced with a solution of NaBH4 in ethanol. In the chemisorption experiment, saturation of the metal surface was achieved at a CO/Pd molar ratio as low as 0.02. For sake of comparison, a Pd/Si02 material (1.2% w/w) was exposed to CO under the same conditions and saturation was achieved at a CO/Pd molar ratio around 0.5. These observations clearly demonstrate that whereas palladium(II) is accessible to the reactant under solid-liquid conditions, when a swollen polymer layer forms beneath the pore surface, this is not true for palladium metal under gas-solid conditions, when swelling of the pore walls does not occur. In spite of this, it was reported that the treatment of dry resins containing immobilized metal precursors [92,85] with dihydrogen gas is an effective way to produce pol-5mer-supported metal nanoclusters. This could be the consequence of the small size of H2 molecules, which... 

Other solutions to dealing with interferences in the detection of H O have included the use of a copperfll) diethyldithiocarbamate precolumn to oxidize the sample before it reaches the immobilized enzyme, as well as the use of a palladium/gold sputtered electrode which catalyzes the oxidation of hydrogen peroxide In addition, peroxidase has been used to catalyze the reaction between hydrogen peroxide and iodide ferrocyanide and organo-fluorine compounds Am-... 

Cationic palladium(II) complexes are homogeneous catalysts for both intramolecular and inter-molecular hydroamination reactions.267 Palladium species immobilized on silica can be prepared by the simple addition of alkyl- or hydroxopalladium(II) complexes to partially dehydroxylated silica. The silica-bound species are more stable than their molecular precursors and are efficient catalysts for the cyclization of aminoalkynes.268... 

Didgikar MR, Roy D, Gupta SP, Joshi SS, Chaudhari RV (2010) Immobilized palladium nanoparticles catalyzed oxidative carbonylation of amines. Ind Eng Chem Res 49 1027-1032... 

Supported palladium catalysts for fine chemicals synthesis are generally based on metal particles. Nevertheless, a few examples are reported of the use of supported complexes as catalysts for the Heck reaction (see Chapter 9.6). Nearly all the possible immobilization methods have been tested for this reaction. 

Apart from examples involving Suzuki reactions with standard soluble palladium catalysts, there is a growing number of publications reporting the use of immobilized, recyclable palladium catalysts for carrying out Suzuki and other cross-cou-... 

Scheme 6.28 Suzuki couplings involving immobilized palladium catalysts.

The readily prepared immobilized phosphoramidite could be used to efficiently synthesize oligodeoxyribonucleotides with modified thymidine residues. Whereas the effect of microwave irradiation on the deprotection by exposing the strand to tet-rakis-triphenylphosphine palladium(O) and diethylammonium bicarbonate was only small using dichloromethane as solvent, complete removal of the alloc group was achieved in N,N-dimethylformamide within 10 min at 80 °C (Scheme 7.30). After the reaction, the solid-supported product was washed with N,N-dimethylformamide and dichloromethane and dried, before being subjected to acylation. The coupling... 

Similar Suzuki couplings have been performed by Hu and coworkers utilizing a poly(dicyclohexylcarbodiimide)/palladium nanoparticle composite [152]. This PDHC-Pd catalyst showed remarkable activity and stability under microwave irradiation. Near quantitative conversion (95% isolated yield) was obtained after 40 min of microwave heating of a mixture of iodobenzene with phenylboronic acid in dioxane. Re-using the immobilized catalyzed showed no significant loss of efficiency, as the fifth cycle still furnished a 90% isolated yield of the desired biphenyl. 

Fig. 2. Scanning electron micrograph showing a natural microbial biofilm developed on surface of immobilized surface when dimethylphthalate was used as the sole source of carbon and energy after dehydration and critical-point dried and coating with palladium and gold (unpublished results). 

The first rhodium-catalyzed reductive cyclization of enynes was reported in I992.61,61a As demonstrated by the cyclization of 1,6-enyne 37a to vinylsilane 37b, the rhodium-catalyzed reaction is a hydrosilylative transformation and, hence, complements its palladium-catalyzed counterpart, which is a formal hydrogenative process mediated by silane. Following this seminal report, improved catalyst systems were developed enabling cyclization at progressively lower temperatures and shorter reaction times. For example, it was found that A-heterocyclic carbene complexes of rhodium catalyze the reaction at 40°C,62 and through the use of immobilized cobalt-rhodium bimetallic nanoparticle catalysts, the hydrosilylative cyclization proceeds at ambient temperature.6... 

The use of dispersed or immobilized transition metals as catalysts for partial hydrogenation reactions of alkynes has been widely studied. Traditionally, alkyne hydrogenations for the preparation of fine chemicals and biologically active compounds were only performed with heterogeneous catalysts [80-82]. Palladium is the most selective metal catalyst for the semihydrogenation of mono-substituted acetylenes and for the transformation of alkynes to ds-alkenes. Commonly, such selectivity is due to stronger chemisorption of the triple bond on the active center. 

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