Rhodium complexes catalytic activity

The metal complexes most often studied as polymer-bound catalysts have been Rh(I) complexes, such as analogues of Wilkinson s complex. The catalytic activity of a bound metal complex is nearly the same as that of the soluble analogue. Rhodium complexes are active for alkene hydrogenation, alkene hydroformylation, and, in the presence of CH3I cocatalyst, methanol carbonylation, etc. Polymer supports thus allow the chemistry of homogeneous catalysis to take place with the benefits of an insoluble, easily separated catalyst . ... 

The strategy of the catalyst development was to use a rhodium complex similar to those of the Wilkinson hydrogenation but containing bulky chiral ligands in an attempt to direct the stereochemistry of the catalytic reaction to favor the desired L isomer of the product (17). Active and stereoselective catalysts have been found and used in commercial practice, although there is now a more economical route to L-dopa than through hydrogenation of the prochiral precursor. 

Asymmetric hydrosilylation can be extended to 1,3-diynes for the synthesis of optically active allenes, which are of great importance in organic synthesis, and few synthetic methods are known for their asymmetric synthesis with chiral catalysts. Catalytic asymmetric hydrosilylation of butadiynes provides a possible way to optically allenes, though the selectivity and scope of this reaction are relatively low. A chiral rhodium complex coordinated with (2S,4S)-PPM turned out to be the best catalyst for the asymmetric hydrosilylation of butadiyne to give an allene of 22% ee (Scheme 3-20) [59]. 

The most recent catalysts that operate under thermal conditions were then based on the premise that a Cp M fragment with ligands that dissociate under thermal conditions could be a catalyst for alkane borylation. After a brief study of Cp IrH4 and Cp Ir(ethylene)2, Dr. Chen studied related rhodium complexes. Ultimately, he proposed that the Cp Rh(ri" -C6Me6) complex would dissociate CeMce as an iimocent side product, and that Cp Rh(Bpin)2 from oxidative addition of pinBBpin (pin=pinacolate) would be the active catalyst. The overall catalytic... 

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. 

Complexation of (124) and (125) with [ Rh(COD)Cl 2] in the presence of Si(OEt)4, followed by sol-gel hydrolysis condensation, afforded new catalytic chiral hybrid material. The catalytic activities and selectivities of these solid materials have been studied in the asymmetric hydro-gen-transfer reduction of prochiral ketones and compared to that of the homogeneous rhodium complexes containing the same ligands (124) and (125) 307... 

A few sulfonated bidentate ligands have been used for which the coordination behavior has been well established for their nonsulfonated analogs the sulfonated ligands showed a behavior that was very much the same as that of their parent ligands in organic solvents. NAPHOS as in rhodium complex (127) behaves the same as BISBI (58), as does its sulfonated analog BINAS (128), which was developed and extensively studied by Herrmann and co-workers.410"413 The catalytically active rhodium complexes [HRh(CO)2(P-P)] of NAPHOS and BINAS have been characterized by IR and NMR spectroscopy.414... 

The synthesis, aggregation behavior, and catalytic activity of Rh complexes of Xantphos derivatives (129) with surface-active pendant groups have been described.416 The complex [HRh(CO)(TPPTS)3] was used as a catalyst precursor in the hydroformylation of 1-butene, 1-octene, and styrene under biphasic reaction conditions 417 The two-phase hydroformylation of buta-1,3-diene with [HRh(CO)(TPPTS)3], with excess TPPPS, gives high yields of C5-monoaldehydes.418 The coordination behavior of the catalytic species HRh(130)(CO)2] was studied by HP NMR spectroscopy which showed the desired bis-equatorial coordination of the ligand to the rhodium center.419... 

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... 

Some of the hydroarylation product is also observed substituted anilines afford the two products to varying degrees (Equation (15)). The closely related rhodium complexes [Rh(PCy3)2Cl]2, [Rh(dmpe)Cl]2 (where dmpe= l,2-bis(dimethylphosphino)ethane), and [Rh(C8H14)Cl]2 show essentially no catalytic activity.166 Application of [Rh(PEt3)2Cl]2 to the reaction of aniline with styrene gives a mixture of hydroamination and oxidative amination products, the latter predominating.167 Other related rhodium-catalyzed amination reactions (oxidative amination) have been reported.168 169... 

In one such procedure a rhodium complex concentrate prepared from a 400 ppm rhodium containing hydroformylation catalyst solution, for which catalytic activity had declined to about 30 percent of its initial value, was concentrated in a wiped-film evaporator to about 27,700 ppm rhodium. This concentrate was oxygenated with tertbu-tylhydroperoxide. After isolation and treatment with triphenylphosphine, a 70% yield of [HRh(CO)(PPh3)3] was obtained.[41]... 

Arya et al. used solid phase synthesis to prepare immobilised dendritic catalysts with the rhodium centre in a shielded environment to mimic nature s approach of protecting active sites in a macromolecular environment (e.g. catalytic sites inside enzymes) [51], Two generations PS immobilised rhodium-complexed dendrimers, 6 and the more shielded 7, were synthesised.The PS resin immobilised rhodium-complexed dendrimers were used in the hydroformylation of styrene, p-methoxystyrene, vinyl acetate and vinyl benzoate using a total pressure of 70 bar 1 1 CO/H2 at 45 °C in CH2C12. 

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