Phosphine-metal complexes rhodium

Phosphines. Polymeric phosphines exhibit strong metal-binding properties. Nonpolymeric phosphines, in particular triphenylphosphine, are employed as ligands for cobalt and rhodium in hydroformylation catalysts used in plasticizer manufacture. Extensive efforts have been made to attach phosphine-metal complexes to polymers in order to facilitate catalyst recovery and enhance selectivity... 

Although trialkyl- and triarylbismuthines are much weaker donors than the corresponding phosphoms, arsenic, and antimony compounds, they have nevertheless been employed to a considerable extent as ligands in transition metal complexes. The metals coordinated to the bismuth in these complexes include chromium (72—77), cobalt (78,79), iridium (80), iron (77,81,82), manganese (83,84), molybdenum (72,75—77,85—89), nickel (75,79,90,91), niobium (92), rhodium (93,94), silver (95—97), tungsten (72,75—77,87,89), uranium (98), and vanadium (99). The coordination compounds formed from tertiary bismuthines are less stable than those formed from tertiary phosphines, arsines, or stibines. 

Phosphine, methyl-n-propylphenyl-rhodium complexes asymmetric hydrogenation, 6,250 Phosphine, neomenthyldiphenyl-rhodium complexes asymmetric hydrogenation, 6,250 Phosphine, phenyl-, 2,992 Phosphine, o-phenylenebis(dimethyl-, 2,993 Phosphine, p-phenylenebis(diphenyl-, 2,993 Phosphine, seleno-metal complexes, 2,664 bidentatc, 2, 664 Phosphine, triaryl-photographic stabilizer, 6,103 Phosphine, tributyl-, 2, 992 oxide... 

Chiral phosphine based transition metal complexes are nsed as a powerful tool for asymmetric synthesis (3). A fundamental mechanistic nnderstanding is required for rhodium and mthenium catalyzed reactions. The starting point of those investigations was the clear and detailed stractnral description of the isolated pre catalyst system. 

Rhodium(I) complexes anchored by phosphine ligands usually have high selectivity but low stability.270-273 One of the possible way to tackle this problem is to bond the metal complexes by oxygen-containing anchoring ligands (14 in Fig. 7.12).274 275... 

Some general reviews on hydrogenation using transition metal complexes that have appeared within the last five years are listed (4-7), as well as general reviews on asymmetric hydrogenation (8-10) and some dealing specifically with chiral rhodium-phosphine catalysts (11-13). The topic of catalysis by supported transition metal complexes has also been well reviewed (6, 14-29), and reviews on molecular metal cluster systems, that include aspects of catalytic hydrogenations, have appeared (30-34). 

In most cases the catalytically active metal complex moiety is attached to a polymer carrying tertiary phosphine units. Such phosphinated polymers can be prepared from well-known water soluble polymers such as poly(ethyleneimine), poly(acryhc acid) [90,91] or polyethers [92] (see also Chapter 2). The solubility of these catalysts is often pH-dependent [90,91,93] so they can be separated from the reaction mixture by proper manipulation of the pH. Some polymers, such as the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers, have inverse temperature dependent solubihty in water and retain this property after functionahzation with PPh2 and subsequent complexation with rhodium(I). The effect of temperature was demonstrated in the hydrogenation of aqueous allyl alcohol, which proceeded rapidly at 0 °C but stopped completely at 40 °C at which temperature the catalyst precipitated hydrogenation resumed by coohng the solution to 0 °C [92]. Such smart catalysts may have special value in regulating the rate of strongly exothermic catalytic reactions. 

The nature of the metal complex can have a profound influence on the rate of hydrogenation, and, even in cases where similar complexes have been prepared by different routes, considerable differences in reactivities can be observed. Thus, the effectiveness of rhodium(I) complexes on phosphinated polystyrene decreases in the order, (21, 76) ... 

Support-bound transition metal complexes have mainly been prepared as insoluble catalysts. Table 4.1 lists representative examples of such polymer-bound complexes. Polystyrene-bound molybdenum carbonyl complexes have been prepared for the study of ligand substitution reactions and oxidative eliminations [51], Moreover, well-defined molybdenum, rhodium, and iridium phosphine complexes have been prepared on copolymers of PEG and silica [52]. Several reviews have covered the preparation and application of support-bound reagents, including transition metal complexes [53-59]. Examples of the preparation and uses of organomercury and organo-zinc compounds are discussed in Section 4.1. 

Hydrosilylation of various carbonyl compounds, enones and related functional groups catalyzed by Group VIII transition metal complexes, especially phosphine-rhodium complexes, have been extensively studied1,3, and the reactions continue to serve as useful methods in organic syntheses. 

The group of Van Leeuwen has reported the synthesis of a series of functionalized diphenylphosphines using carbosilane dendrimers as supports. These were applied as ligands for palladium-catalyzed allylic substitution and amination, as well as for rhodium-catalyzed hydroformylation reactions [20,21,44,45]. Carbosilane dendrimers containing two and three carbon atoms between the silicon branching points were used as models in order to investigate the effect of compactness and flexibility of the dendritic ligands on the catalytic performance of their metal complexes. Peripherally phosphine-functionalized carbosilane dendrimers (with both monodentate... 

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