Rhodium catalysts, for hydrogenation

Ans. (a) Rhodium catalysts for hydrogenation require ligands capable of stabilizing a low oxidation state, (b) Oxygen atom donors oxidize phosphine to phosphine oxide. Also phosphines are not the best ligands to stabilize... 

Lopez-Castillo, Z. K. Flores, R. Kani, I. Fackler, Jr.,J. P. Akgerman, A. Fluoroacrylate Copolymer Supported Rhodium Catalysts for Hydrogenation Reactions in Supercritical Carbon Dioxide. Ind. Eng. Chem. Res., 2002,41, 3075-3080... 

Closely related to the use of rhodium catalysts for the hydrogenation of phenols is their use in the reduction of anilines. The procedure gives details for the preparation of the catalyst and its use to carry out the low-pressure reduction of /j-aminobenzoic acid. Then, as in the preceding experiment, advantage is taken of the formation of a cyclic product to carry out the separation of a mixture of cis and trans cyclohexyl isomers. 

The rhodium complexes are excellent catalysts for hydrogenation of NBR. At low temperature and pressure, high catalyst concentrations are used to obtain a better rate of reactions. Due to higher selectivity of the reaction, pressure and temperature can be increased to very high values. Consequently the rhodium concentration can be greatly reduced, which leads to high turnover rates. The only practical drawback of Rh complex is its high cost. This has initiated the development of techniques for catalyst removal and recovery (see Section VU), as well as alternate catalyst systems based on cheaper noble metals, such as ruthenium or palladium (see Sections IV.A and B). 

Palladium is used as a catalyst for hydrogenation reactions in the food industry, and a rhodium catalyst is used in... 

The use of rhodium catalysts for the synthesis of a-amino acids by asymmetric hydrogenation of V-acyl dehydro amino acids, frequently in combination with the use of a biocatalyst to upgrade the enantioselectivity and cleave the acyl group which acts as a secondary binding site for the catalyst, has been well-documented. While DuPhos and BPE derived catalysts are suitable for a broad array of dehydroamino acid substrates, a particular challenge posed by a hydrogenation approach to 3,3-diphenylalanine is that the olefin substrate is tetra-substituted and therefore would be expected to have a much lower activity compared to substrates which have been previously examined. 

Laska, U., Frost, C.G., Plucinski, P.K. and Price, G.J. (2008) Rhodium containing magnetic nanoparticles effective catalysts for hydrogenation and the 1 4-addition of boronic acids. Catalysis Letters, 122 (1-2), 68-75. 

The most commonly used catalysts for hydrogenation (finely divided platinum, nickel, palladium, rhodium, and ruthenium) apparently serve to adsorb hydrogen molecules on their surface. 

Catalysts for hydrogenation can be also supported on ion exchange resins. For example, rhodium(III) chloride, attached to a 3-carboxy-butenolic acid/DVB cation exchange resin with... 

Prochiral imines can be hydrogenated to the corresponding amines with extremely high enan-tioselectivities in H20/ethyl ethanoate biphasic systems, using Rh1 complexes of sulfonated phosphines 342 The cationic rhodium complex [Rh(NBD)(131)]+ was an active catalyst for hydrogenation of 2-ethanamido-propenoic acid in aqueous solution.343... 

The monosulfonated PPh derivative, Ph2P(m-C6H4S03K) (DPM) and its rhodium complex, HRh(CO)(DPM)3 have been synthesized and characterized by IR and NMR spectroscopic techniques. The data showed that the structure was similar to [HRh(CO)(PPh3)3]. The catalytic activity and selectivity of [HRh(CO)(DPM)3] in styrene hydroformylation were studied in biphasic catalytic systems.420 421 Rh1 complexes [Rh(acac)(CO)(PR3)] with tpa (131), cyep (132), (126), ompp (133), pmpp (134), tmpp (135), PPh2(pyl), PPh(pyl)2, and P(pyl)3 were characterized with NMR and IR spectra. Complexes with (131), (132), and (126) were catalysts for hydrogenation of C—C and C—O bonds, isomerization of alkenes, and hydroformylation of alkenes.422 Asymmetric hydroformylation of styrene was performed using as catalyst precursor [Rh(//-0 Me)(COD)]2 associated with sodium salts of m-sulfonated diarylphosphines.423... 

Immobilization of homogeneous catalysts for hydrogenation reactions concerns essentially enan-tioselective hydrogenations, important for the synthesis of fine chemicals (see Chapter 9.2). The pioneering work of Pugin et al.131 concerns the synthesis of a rhodium-based catalyst, with a diphosphine-pyrrolidine-based ligand for the hydrogenation of methylacetamide cinnamate (Equation(8)). 

Finally, other rhodium catalysts for the selective diene hydrogenation worth mentioning include [RhCl(PPh3)3] (64), [RhCl(nbd)]2 (65), and the catalytic sys-... 

The first report of rhodium catalysts for aldehyde reduction came from Marko who reported the use of RhCl3 3H20 under hydroformylation conditions [9]. It was suggested that the active species were rhodium carbonyls, and the catalyst system was successfully utilized in the hydrogenation of ethanal, propanal, and benzalde-... 

To date, reports have involved palladium catalysts for Suzuki and Sono-gashira coupling reactions [63-66], rhodium catalysts for silylations of alcohols by trialkylsilanes [67,68], and tin-, hafnium-, and scandium-based Lewis acid catalysts for Baeyer-Villiger and Diels-Alder reactions [69]. Regardless of exact mechanism, this recovery strategy represents an important direction for future research and applications development. Finally, a particularly elegant protocol where CO2 pressure is used instead of temperature to desorb a fluorous rhodium hydrogenation catalyst from fluorous silica gel deserves emphasis [28]. 

The discovery of Wilkinson complex, RhCl[P(C6H5)3]3, acting as an effective catalyst for hydrogenation of olefins opened the door for developing asymmetric reaction catalyzed by rhodium complexes with a chiral phosphine ligand. 

Rh203 is used to make rhodium metal and its various salts. Also, the oxide is a catalyst for hydrogenation. 

Sanchez, F., Iglesias, M., Corma, A. and Delpino, C. New rhodium complexes anchored on silica and modified Y-zeolite as efficient catalysts for hydrogenation of olefins, J. Mol. Catal., 1991, 70, 369-379. 

Chiral hydrogenation catalysts. Rhodium and ruthenium phosphines are effective homogeneous catalysts for hydrogenation. Chiral ligands can be attached to accomplish asymmetric induction, the creation of a new asymmetric carbon as mostly one enantiomer. 

The catalyst in each of these three reductions is a different metal. Palladium and platinum are the most commonly used metal catalysts for hydrogenation, but hydrogenation can also work with nickel, rhodium, or ruthenium. The choice of catalyst depends on the compound to be reduced. 

Riesz and Weber compared the selectivities of commercial platinum, palladium, rhodium, and nickel catalysts for hydrogenation of linolenic components in soybean oil.110 Representative results are summarized in Table 3.8. Certain platinum metal catalysts showed higher selectivities than nickel catalysts, as indicated by the values of SL (A in Scheme 3.13) = 2.4-2.7. Generally, nickel catalysts showed selectivities... 

Kumada et al. have examined a number of chiral ferrocenylphosphines as ligands for asymmetric reactions catalyzed by transition metals. They are of interest because they contain a planar element of chirality as well as an asymmetric carbon atom. They were first used in combination with rhodium catalysts for asymmetric hydrosilylation of ketones with di- and trialkylsilanes in moderate optical yields (5-50%). High stereoselectivity was observed in the hydrogenation of a-acetamidoacrylic acids (equation 1) with rhodium catalysts and ferrocenylphosphines. ... 

Bhore, N. A. Modifiers in Rhodium Catalysts for Carbon Monoxide Hydrogenation Structure - Activity Relationships. RlD. Thesis, University of Delaware, 1989. Hall, W. K.., Proceedings of the Climax Fourth International Conference on the Chemistry and Uses of Molybdenum, Barry and Mitchell, Eds., Climax Molybdenum Co., Ann Aibor, MI, p. 224 - 233 (1982). 

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