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Catalytic hydroformylation of olefins

The catalytic hydroformylation of olefins is discussed in Chapter 5. The reaction of propylene with CO and H2 produces n-butyraldehyde as the main product. Isobutyraldehyde is a by-product °... [Pg.232]

A novel catalyst, RhH(CO)(P(p-CFjPh)j)3, was synthesized for the homogeneous catalytic hydroformylation of olefins in supercritical carbon dioxide. The incorporation of p-(trifluoromethyl) groups in the conventional hydroformylation catalyst, HRhCO(PPh3)3, provided enhanced solubility in supercritical carbon dioxide while maintaining catalyst activity and selectivity in the hydroformylation of 1-octene. The reaction rate showed a first-order dependence on the catalyst concentration. The total system pressure had no effect on either the reaction rate or selectivity. However, selectivity was found to depend on the concentration of the catalyst [63]. [Pg.418]

Equation (9.9) is crucial in catalytic hydroformylation of olefins, and Orchin and Rupilius were perhaps the first authors to properly illustrate the side-on bonded H2 ligand in analogy to olefin binding and propose M - H2 backbonding as an important component to H2 activation.22 f2-H2 intermediates have not been detected in such reactions, but calculations show that a -bond metathesis pathway is possible (see Section 4.12). An if1 bridging H2 is proposed in the transition state for addition of H2 to the d1 tetramesitylporphyrin complex Rh(tmp) to give d6 RhH(tmp).23... [Pg.265]

Table 2.34. Selected examples of catalytic hydroformylation of olefines by metal clusters. Table 2.34. Selected examples of catalytic hydroformylation of olefines by metal clusters.
Lu SJ, Li XD, Wang AL. A new chiral diphosphine ligand and its asymmetric induction in catalytic hydroformylation of olefins. Catal. Today 2000 63 531 536. [Pg.418]

Concern for the conservation of energy and materials maintains high interest in catalytic and electrochemistry. Oxygen in the presence of metal catalysts is used in CUPROUS ION-CATALYZED OXIDATIVE CLEAVAGE OF AROMATIC o-DIAMINES BY OXYGEN (E,Z)-2,4-HEXADIENEDINITRILE and OXIDATION WITH BIS(SALI-CYLIDENE)ETHYLENEDIIMINOCOBALT(II) (SALCOMINE) 2,6-DI-important industrial method, is accomplished in a convenient lab-scale process in ALDEHYDES FROM OLEFINS CYCLOHEXANE-CARBOXALDEHYDE. An effective and useful electrochemical synthesis is illustrated in the procedure 3,3,6,6-TETRAMETHOXY-1,4-CYCLOHEX ADIENE. ... [Pg.129]

Cationic phosphine ligands containing guanidiniumphenyl moieties were originally developed in order to make use of their pronounced solubility in water [72, 73]. They were shown to form active catalytic systems in Pd-mediated C-C coupling reactions between aryl iodides and alkynes (Castro-Stephens-Sonogashira reaction) [72, 74] and Rh-catalyzed hydroformylation of olefins in aqueous two-phase systems [75]. [Pg.237]

Abstract This chapter presents the latest achievements reported in the asymmetric hydroformylation of olefins. It focuses on rhodium systems containing diphosphites and phosphine-phosphite ligands, because of their significance in the subject. Particular attention is paid to the mechanistic aspects and the characterization of intermediates in the hydroformylation of vinyl arenes because these are the most important breakthroughs in the area. The chapter also presents the application of this catalytic reaction to vinyl acetate, dihydrofurans and unsaturated nitriles because of its industrial relevance. [Pg.44]

Rh, are the base of active catalysts for CO hydrogenation and the hydroformylation of olefins. The presence of several promoters modifies their catalytic behavior and synergic effects on the base-metal have been observed Table 8.5 illustrates several examples in which homonuclear or heteronuclear carbonyl compounds have been used in the preparation of Co- or Co-Rh-based catalysts for the CO hydrogenation and/or hydroformylation reactions. [Pg.331]

This preparation is an illustration of the hydroformylation of olefins (oxo synthesis). The reaction occurs in the presence of soluble catalytic complexes containing metals of Group VIII of the periodic system. Although the metal originally used by Roelen and still largely used in the industry for the production of aliphatic aldehydes and alcohols is cobalt, the most active and selective catalysts are rhodium-containing compounds. The catalytic activity of the other Group VIII metals is in... [Pg.76]

The variable-temperature NMR spectra help to explain the catalytic properties of the dppp complex system which were outlined previously in Table I. The reduced catalytic activity compared with the tris(triphenylphosphine) complex system is apparently due to the reduced dissociation of the cyclic complexes. For example, the 90°C spectra of Figures 3 and 13, clearly show that the ligand-exchange rate is much slower in the case of dppp. However, temperature-dependent ligand exchange of the monocyclic complex occurs and leads to cis-bisphosphine species that catalyze the hydroformylation of olefins at minimal partial pressures of CO. The hydroformylation rate of the dppp system is faster at 1 atm CO pressure than that of the dppe system. Of course, such hydroformylations are nonselective due to the cis-stereochemistry. [Pg.70]

The hydroformylation of olefins is one of the largest and most prominent industrial catalytic processes, producing millions of tons of aldehydes annually [102]. Initially, cobalt-carbonyl species were used as catalyst, though rhodium complexes modified by special ligands, usually phosphines, are predominantly used nowadays. Over the last two decades, continued development of new phosphine and phosphite ligands has allowed significant advances in hydroformylation chemistry, especially with respect to catalyst selectivity and stability [103]. [Pg.138]

The catalytic hydroformylation of long-chain and branched olefins remains a challenge as the activity of the water-soluble catalysts decreases rapidly with increasing chain length of the olefin. Extensive work has been undertaken to overcome these limitations (74). [Pg.50]

TABLE 8 Data Characterizing Catalytic Hydroformylation of Various Olefins with Rhodium Polyethylene Glycolate Complex.°... [Pg.51]

The hydroformylation of olefins is the most widely used homogeneous catalytic process using CO gas. It involves the addition of one molecule of CO and H2 to an olefin in the presence of a transition metal catalyst, most frequently based on cobalt or rhodium, resulting in the formation of an aldehyde. Generally, it is believed that the activation of H2 in cobalt-catalysed hydroformylation occurs on the unsaturated species Co2(CO)7 or Co(acylXCO)3 formed by the following reactions ... [Pg.221]

Among the most significant developments in the field of catalysis in recent years have been the discovery and elucidation of various new, and often novel, catalytic reactions of transition metal ions and coordination compounds 13, 34). Examples of such reactions are the hydrogenation of olefins catalyzed by complexes of ruthenium (36), rhodium (61), cobalt (52), platinum (3, 26, 81), and other metals the hydroformylation of olefins catalyzed by complexes of cobalt or rhodium (Oxo process) (6, 46, 62) the dimerization of ethylene (i, 23) and polymerization of dienes (15, 64, 65) catalyzed by complexes of rhodium double-bond migration in olefins catalyzed by complexes of rhodium (24,42), palladium (42), cobalt (67), platinum (3, 5, 26, 81), and other metals (27) the oxidation of olefins to aldehydes, ketones, and vinyl esters, catalyzed by palladium chloride (Wacker process) (47, 48, 49,... [Pg.1]

Homogeneous catalytic reactions with the catalyst being dissolved in the same phase as the reactants and products in a homogeneous reaction medium. Here the catalyst is uniformly distributed throughout the system, e.g., the hydroformylation of olefins in the presence of dissolved Co or Rh carbonyls. [Pg.10]


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See also in sourсe #XX -- [ Pg.729 ]




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