Carbonyl exchange rhodium

One of the only examples of a commercial process using immobilised homogeneous catalysts comprises an anionic rhodium complex [RhI2(CO)2] that is bound via ionic interactions to an ion exchange resin [3] and is used for the carbonylation of methanol. 

An alternative strategy for catalyst immobilisation uses ion-pair interactions between ionic catalyst complexes and polymeric ion exchange resins. Since all the rhodium complexes in the catalytic methanol carbonylation cycle are anionic, this is an attractive candidate for ionic attachment. In 1981, Drago et al. described the effective immobilisation of the rhodium catalyst on polymeric supports based on methylated polyvinylpyridines [48]. The activity was reported to be equal to the homogeneous system at 120 °C with minimal leaching of the supported catalyst. The ionically bound complex [Rh(CO)2l2] was identified by infrared spectroscopic analysis of the impregnated resin. 

A mechanistic study by Haynes et al. demonstrated that the same basic reaction cycle operates for rhodium-catalysed methanol carbonylation in both homogeneous and supported systems [59]. The catalytically active complex [Rh(CO)2l2] was supported on an ion exchange resin based on poly(4-vinylpyridine-co-styrene-co-divinylbenzene) in which the pendant pyridyl groups had been quaternised by reaction with Mel. Heterogenisation of the Rh(I) complex was achieved by reaction of the quaternised polymer with the dimer, [Rh(CO)2l]2 (Scheme 11). Infrared spectroscopy revealed i (CO) bands for the supported [Rh(CO)2l2] anions at frequencies very similar to those observed in solution spectra. The structure of the supported complex was confirmed by EXAFS measurements, which revealed a square planar geometry comparable to that found in solution and the solid state. The first X-ray crystal structures of salts of [Rh(CO)2l2]" were also reported in this study. 

In an effort to assign the bands to ee and ae isomers the (thixantphos)Rh(CO)2D complex was measured for comparison. Upon H/D exchange, only Vi and v3 shift to lower wavenumbers (respectively 18 and 14 cm-1), and therefore, these two bands are assigned to the carbonyl frequencies of the ee complex. The two bands that do not shift, v2 and v4, belong to the ae complex. From the disappearance of a low-frequency shoulder upon H/D exchange, it can be concluded that one of the rhodium hydride vibrations is partly hidden under v4. 

The exponential decay of the strongest carbonyl absorption is presented in Figure 6.16A. The natural logarithm of the relative absorption of the carbonyl frequency at 2020 cm versus time is presented in Figure 6.16B, indicative of first-order kinetics in the rhodium concentration and the pressure of FI2 and the H/D exchange rate was 1140 h Although the H/D exchange reaction was very... 

Under mild conditions, hydroformylation of olefins with rhodium carbonyl complexes selectively produces aldehydes. A one-step synthesis of oxo alcohols is possible using monomeric or polymeric amines, such as dimethylbenzylamine or anion exchange resin analog to hydrogenate the aldehyde. The rate of aldehyde hydrogenation passes through a maximum as amine basicity and concentration increase. IR data of the reaction reveal that anionic rhodium carbonyl clusters, normally absent, are formed on addition of amine. Aldehyde hydrogenation is attributed to enhanced hydridic character of a Rh-H intermediate via amine coordination to rhodium. 

The tris(triphenylphosphine) rhodium carbonyl hydride complex also was used via ligand exchange to obtain known chelate complexes of bisphosphines... 

When the P/Rh ratio was only 3.3, major amounts of the rhodium were in the form of fast exchanging more highly carbonylated species. 

Treatment of the ion-exchanged RhNaX catalyst with hydrogen (205) results in almost complete reduction of Rh3+ to Rh° with a consequent much reduced carbonylation activity, whereas ether formation remains virtually unaffected. These results demonstrate that the dehydration activity is a function of the support only and that cationic rather than zero-valent rhodium is the active entity for the carbonylation reaction. 

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