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Rhodium complexes triphenylphosphine

The use of a catalyst such as cadmium oxide increases the yield of dibasic acids to about 51% of theoretical. The composition of the mixed acids is about 75% C-11 and 25% C-12 dibasic acids (73). Reaction of undecylenic acid with carbon monoxide using a triphenylphosphine—rhodium complex as catalyst gives 11-formylundecanoic acid, which, upon reaction with oxygen in the presence of Co(II) salts, gives 1,12-dodecanedioic acid in 70% yield (74). [Pg.63]

In the practice of gas recycle hydroformylation [7], rhodium complex and triphenylphosphine are dissolved in a suitable solvent. The reactor is pressurized with the... [Pg.12]

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]... [Pg.36]

The last example of a dendritic effect discussed in this chapter is the use of core-functionalized dendritic mono- and diphosphine rhodium complexes by Van Leeuwen el al. [45] Carbosilane dendrimers were functionalized in the core with Xantphos, bis(diphenylphosphino)ferrocene (dppf) and triphenylphosphine (Figures 4.22, 4.32 and 4.33). [Pg.94]

The rate of hydroformylation was found to vary in a nonlinear fashion as a function of triphenylphosphine concentration. A maximum in rate was noted at a triphenylphosphine/HRh(CO)(PPh3)3 weight ratio of (5-10) 1, as illustrated in Fig. 7. A maximum in selectivity to linear aldehyde was noted at about a 5 1 ratio, and no significant further increase was noted up to a 50 1 ratio of triphenylphosphine to rhodium complex. [Pg.27]

During the late 1960s, Homer et al. [13] and Knowles and Sabacky [14] independently found that a chiral monodentate tertiary phosphine, in the presence of a rhodium complex, could provide enantioselective induction for a hydrogenation, although the amount of induction was small [15-20]. The chiral phosphine ligand replaced the triphenylphosphine in a Wilkinson-type catalyst [10, 21, 22]. At about this time, it was also found that [Rh(COD)2]+ or [Rh(NBD)2]+ could be used as catalyst precursors, without the need to perform ligand exchange reactions [23]. [Pg.746]

In 1986 a new process came on stream employing a two-phase system with rhodium in a water phase and the substrate and the product in an organic phase. For propene this process is the most attractive one at present. The catalyst used is a rhodium complex with a sulphonated triarylphosphine, which is highly water-soluble (in the order of 1 kg of the ligand "dissolves" in 1 kg of water). The ligand, tppts (Figure 8.6), forms complexes with rhodium that are most likely very similar to the ordinary triphenylphosphine complexes (i.e. RhH(CO)(PPh3)3). [Pg.150]

This complex easily looses CO, which enables co-ordination of a molecule of alkene. As a result the complexes with bulky phosphite ligands are very reactive towards otherwise unreactive substrates such as internal or 2,2-dialkyl 1-alkenes. The rate of reaction reaches the same values as those found with the triphenylphosphine catalysts for monosubstituted 1-alkenes, i.e. up to 15,000 mol of product per mol of rhodium complex per hour at 90 °C and 10-30 bar. When 1-alkenes are subjected to hydroformylation with these monodentate bulky phosphite catalysts an extremely rapid hydroformylation takes place with turnover frequencies up to 170,000 mole of product per mol of rhodium per hour [65], A moderate linearity of 65% can be achieved. Due to the very fast consumption of CO the mass transport of CO can become rate determining and thus hydroformylation slows down or stops. The low CO concentration also results in highly unsaturated rhodium complexes giving a rapid isomerisation of terminal to internal alkenes. In the extreme situation this means that it makes no difference whether we start from terminal or internal alkenes. [Pg.162]

Hayashi proved the validity of this catalytic cycle by the observation of aU three intermediates and their respective transformations using NMR experiments (Scheme 3.5) [16]. Transmetallation of a phenyl group from boron to rhodium takes place by addi-hon of phenylboronic acid 2 m to hydroxo-rhodium complex 16 in the presence of tri-phenylphosphine to generate the phenylrhodium complex 17. The reaction of 17 with 2-cyclohexenone la gives oxa- j-allylrhodium 18, which is converted immediately into hydroxo-rhodium complex 16 upon addition of water, liberating the phenylation product 3 am. In this NMR study, triphenylphosphine was used to stabilize the phenylrho-dium(I) complex. In the absence of triphenylphosphine, the characterization of the phenyl-rhodium species was unsuccessful. [Pg.60]

The chelating behavior was also evident from H P-NM R experiments. The addition of triphenylphosphine (a) to a catalyst solution of [HRh(CO)2(13 b)] did not affect the complex. Moreover, the addition of 1 equiv. of b to a solution of HRh(CO)2(13) PPhj resulted in the exclusive formation of [HRh(CO)2(13 b)] upon release of free triphenylphosphine. The chelating effect of the supramolecular ligand assembly effectively competes with triphenylphosphine, leading to exclusive formation of the rhodium complex of 13 b. In the complex [HRh(CO)2(13 b) the supramolecular ligand 13 b coordinates in an equatorial-equatorial fashion to the rhodium metal center, whereas the HRh(CO)2(13)PPh3 exists in a mixture of complexes (ee and ea). [Pg.217]

The activity of rhodium complexes with phosphine or phosphite ligands is about three to four orders of magnitude higher than that of cobalt catalysts.21-23 [RhH(CO)(PPh3)3] preformed or prepared in situ has proved to be the active species when triphenylphosphine is used as ligand. Despite the high cost of rhodium, the mild reaction conditions and high selectivities make rhodium complexes the catalyst of choice in hydroformylation. [Pg.372]

Mitsubishi Kasei introduced a process to manufacture isononyl alcohol, an important PVC (polyvinyl chloride) plasticizer, via the hydroformylation of octenes (a mixture of isomers produced by dimerization of the C4 cut of naphtha cracker or FCC processes).95 First a nonmodified rhodium complex exhibiting high activity and selectivity in the formation of the branched aldehyde is used. After the oxo reaction, before separation of the catalyst, triphenylphosphine is added to the reaction mixture and the recovered rhodium-triphenylphosphine is oxidized under controlled conditions. The resulting rhodium-triphenylphosphine oxide with an activity and selectivity similar to those of the original complex, is recycled and used again to produce isononanal. [Pg.379]

The reaction of bis-phenylpropargyl ether (321) with tris(triphenylphosphine)rhodium chloride in benzene or toluene led to the formation of the unusual organometallic compound (322), which can be viewed as a derivative of an oxygen-rhodium pentalene system. Reaction of the rhodium complex (322) with sulfur leads to the corresponding 4,6-diphenyl-l,3-dihydro[3,4-c]furan (323). The selenium and tellurium analogs (324) and (325) were made in a similar manner (Scheme 111) (76LA1448). [Pg.1079]

Homogeneous hydrogenation catalyzed by the four-coordinated rhodium complex, Rh[(C6H5)3P]3Cl, has been particularly well investigated. With this catalyst, the first step is formation of the six-coordinated rhodium hydride of known configuration, 16, in which we abbreviate the ligand, triphenylphosphine, (C6H5)3P, as L ... [Pg.1517]

P-31 NMR Studies of Equilibria and Ligand Exchange in Triphenylphosphine Rhodium Complex and Related Chelated Bisphosphine Rhodium Complex Hydroformylation Catalyst Systems... [Pg.50]

Triphenylphosphine -rhodium complex hydroformylation catalyst systems discovered by Wilkinson and developed by Union Carbide, Davy Powergas, and Johnson Matthey... [Pg.50]

P-31 NMR was a powerful tool in studies correlating the structure of tertiary-phosphine-rhodium chloride complexes with their behavior as olefin hydrogenation catalysts. Triphenylphosphine-rhodium complex hydrogenation catalyst species (1) were studied by Tolman et al. at du Pont and Company (2). They found that tris(triphenylphosphine)rhodium(I) chloride (A) dissociates to tri-phenylphosphine and a highly reactive intermediate (B). The latter is dimerized to tetrakis(triphenylphosphine)dirhodium(I) dichloride (C). [Pg.51]

Applying P-31 NMR to the field of hydroformylation catalysis by triphenylphosphine rhodium complex-based systems is the subject of this chapter. These hydroformylation catalyst systems are of high academic and technological interest. They are effective for hydroformylat-ing 1-olefins at low pressure and temperature and exhibit a high selectivity to n-aldehydes ... [Pg.51]

The studies of Wilkinson et al. included IR and H-l NMR spectroscopy of the intermediate species of this catalyst system (7). This led to recognizing tris(triphenylphosphine)rhodium(I) carbonyl hydride (D) as the key stable rhodium complex. The reactive trans-bis-(triphenylphosphine)rhodium(I) carbonyl hydride (E) resulting via the dissociation of this complex... [Pg.52]

In the spectra of the various solutions containing excess triphenylphosphine, the expected singlet signal at 7.2 ppm appeared. Also present in all of the solutions was a sharp singlet signal at +22.1 ppm, due to triphenylphosphine oxide, which always was formed due to oxidation by the traces of molecular oxygen present. The present rhodium complex system is a very effective catalyst for such oxidations. [Pg.55]

P NMR Studies of Catalytic Intermediates in Triphenylphosphine Rhodium Complex Hydroformylation Systems... [Pg.503]

Decarbonylation of aldoses.2 Although this rhodium complex has been known since 1968 to effect decarbonylation of aldehydes, it has been used for decarbonylation of sugars only recently, probably for lack of a compatible solvent. Actually, this reaction when carried out in N-methyl-2-pyrrolidinone (NMP) at 110-130° is extremely useful in the case of simple aldoses, which are converted to the lower alditol with formation of carbonylchlorobis(triphenylphosphine)rhodium(I). The yields are 75-95%. This method of degradation has the further advantage that protecting groups are not necessary. Deoxyaldoses, particularly 2-deoxyaldoses, are decar-bonylated in 75-99% yield. A disadvantage of this reaction is that a full equivalent of the complex is required. [Pg.87]


See other pages where Rhodium complexes triphenylphosphine is mentioned: [Pg.73]    [Pg.167]    [Pg.141]    [Pg.156]    [Pg.221]    [Pg.345]    [Pg.1037]    [Pg.294]    [Pg.25]    [Pg.174]    [Pg.149]    [Pg.220]    [Pg.173]    [Pg.141]    [Pg.156]    [Pg.141]    [Pg.156]    [Pg.125]    [Pg.143]    [Pg.190]    [Pg.521]    [Pg.13]    [Pg.241]    [Pg.434]    [Pg.55]    [Pg.62]    [Pg.1718]    [Pg.1060]    [Pg.503]   
See also in sourсe #XX -- [ Pg.905 ]

See also in sourсe #XX -- [ Pg.4 , Pg.905 ]




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