Heterogeneous palladium catalysts

The SM reactions catalysed by Miyaura s diphenylphosphine-bounded palladium heterogeneous catalyst (342) Preparation of the catalyst and the cross-coupling reaction of 4-tolylboronic acid (271) with 2-chloro pyridine (149) /139I... 

Birch also illustrated tire difference in selectivity between Wilkinson s catalyst and typical heterogeneous catalysts. Hydrogenation of 1,4-dihydrobenzenes (derived from the "Birch reductions" of arenes) in the presence of Wilkinson s catalyst forms the tetra-substituted alkene product, whereas hydrogenation with classic platinum and palladium heterogeneous catalysts causes disproportionation to form arene byproducts (Equation 15.6). Like the (3-keto alcohol in Equation 15.5, the ester in Equation 15.6 is not reduced. 

Gao H., Angelici R.J. Combination catalysts consisting ofa homogeneous catalyst tethered to a silica-supported palladium heterogeneous catalyst Arene hydrogenation. J. Am. Chem. Soc. 1997 119 6937-6938... 

This section discusses the processes for nitrile rubber hydrogenation developed during past years using a heterogeneous catalyst. The published reports suggest that mostly the palladium catalyst has been used for nitrile... 

In the preceding section, it has been shown that considerable attention has been devoted to palladium as a heterogeneous catalyst. The present section describes the homogeneous palladium catalysts developed for hydrogenation of NBR. The main drive behind the development of various catalyst systems is to find suitable substituents of the Rh catalyst. Palladium complexes are much cheaper as compared with Rh and exhibit comparable activity and selectivity to Rh and Ru complexes. 

In the present chapter, we focus on the catalyst nature in solution using well-defined metal NPs as catal 4 ic precursors it means, soluble (or dispersible) heterogeneous pre-catalysts, as stated by Finke [6]. Some experiments described in the literature concerning the distinction between homogeneous and heterogeneous catalysts are discussed (see Section 3), followed by a particular case studied by us with regard to the catalyst nature in the allylic alkylation reaction, using preformed palladium NPs as catalytic precursors (see Section 4). 

To assess the utility of this resin, we chose to employ it in the evaluation of the heterogeneity of a commercial polymer-entrapped Pd(OAc)2 precatalyst, Pd-EnCat, also sold by Reaxa. This precatalyst was designed with the goal of providing a heterogeneous catalyst that would allow simple removal of palladium from reactions (24-26). PVPy and QTU were first used as poisons in the Heck reaction of iodobenzene and n-butyl acrylate in DMF using PdfC as the palladium... 

The most widely used method for adding the elements of hydrogen to carbon-carbon double bonds is catalytic hydrogenation. Except for very sterically hindered alkenes, this reaction usually proceeds rapidly and cleanly. The most common catalysts are various forms of transition metals, particularly platinum, palladium, rhodium, ruthenium, and nickel. Both the metals as finely dispersed solids or adsorbed on inert supports such as carbon or alumina (heterogeneous catalysts) and certain soluble complexes of these metals (homogeneous catalysts) exhibit catalytic activity. Depending upon conditions and catalyst, other functional groups are also subject to reduction under these conditions. 

Lanthanides in combination with transition metals have been shown to have a positive effect in promoting heterogeneous catalytic reactions. The bimetallic Yb—Pd catalyst obtained from the precursor (pMF)i0Yb2 Pd(CN)4]3 K on a titania surface offers improved performance over a palladium-only catalyst for the reduction of NO by CH4 in the presence of 02.99 100 The structure, shown in Figure 6, consists of two inverted parallel zigzag chains that are connected through the lanthanide atoms by trans-bridging [Pd(CN)4]2- anions.101... 

Once the reaction kinetics were determined and the appropriate reaction conditions were set, the analyses of different catalysts was launched. A variety of different heterogeneous catalysts were evaluated for the deprotection of 20 mmol Cbz-glycine (1, R=-H). Catalysts composed of different platinum group metals supported on activated carbon were evaluated as well as palladium supported on alumina. Figure 5 confirms that Pd supported on activated carbon is indeed the catalyst of choice for this type of hydrogenolysis reaction. 

Typically, the Pd species for Heck couplings are homogeneous catalysts, stabilized by air-sensitive ligands. They present economic and environmental problems regarding separation, regeneration and reuse. These difficulties can be diminished with heterogeneous catalysts that are more easily recoverable from the reaction mixture. As mentioned in Sect. 2.6, a catalyst consisting of palladium metal deposited on por-... 

A similar silastannative cyclization reaction has been extensively studied with 1,6-enynes (Table 9).271-274 Several palladium catalysts including palladium(0)-DBA complex and even a heterogeneous catalyst are effective, whereas Pd(PPh3)4 gives an uncyclized simple adduct predominantly. 

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. 

The addition of dopants is found to have beneficial effects. However, they are not restricted only to transition metals. The hydrogenation of acrylic acid can be promoted significantly by the addition of neodymium ions onto the palladium particles [142], The selective transformation of 3,4-dichloronitrobenzene to the corresponding aniline has been selected to test pre-prepared Pt hydrosols as heterogeneous catalyst precursors (see Figure 3.9) [143],... 

A new class of heterogeneous catalyst has emerged from the incorporation of mono- and bimetallic nanocolloids in the mesopores of MCM-41 or via the entrapment of pro-prepared colloidal metal in sol-gel materials [170-172], Noble metal nanoparticles containing Mex-MCM-41 were synthesized using surfactant stabilized palladium, iridium, and rhodium nanoparticles in the synthesis gel. The materials were characterized by a number of physical methods, showed that the nanoparticles were present inside the pores of MCM-41. They were found to be active catalysts in the hydrogenation of cyclic olefins such as cyclohexene, cyclooctene, cyclododecene, and... 

Kim, S.W. et al., Fabrication of hollow palladium spheres and their successful application to the recyclable heterogeneous catalyst for Suzuki coupling reactions, J. Am. Chem. Soc., 124, 7642, 2002. 

The use of heterogeneous catalysts in this reaction has also been achieved palladium-montmorillonite clays [93] or palladium/activated carbon [94] in the presence of dppb transformed 2-allylphenols into lactones, the regiose-lectivity of the reaction being largely dependant on the nature of the support. Very recently, palladium complexes immobilized onto silica-supported (polyaminoamido)dendrimers were used as catalysts in the presence of dppb for the cyclocarbonylation of 2-allylphenols, 2-allylanilines, 2-vinylphenols, and 2-vinylanilines affording five-, six-, or seven-membered lactones and lactams. Good conversions are realized and the catalyst can be recycled 3-5 times [95]. 

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