Hydroformylation with supported catalysts

Industrial hydroformylation is currently performed in two basic variants the homogeneous processes, where the catalyst and substrate are in the same liquid phase (Shell, UCC, BASF, etc.), and the two-phase process with a water-soluble catalyst (RCH/RP). These processes will be discussed in detail in Section 2.1.1.4. Gas-phase hydroformylation with heterogeneous catalysts plays no role today. The immobilization of homogeneous catalysts will be discussed in Section 3.1.1. Special applications such as SLPC (supported /iquid-phase catalysts) [43] and SAPC (supported aqueous-/7hase catalysts) [44] are not considered further here. Heterogeneous oxo catalysts are not within the scope of this book they are discussed further elsewhere [267]. 

Chiral pyridine addition to cobalt catalysts derived from dicobalt octacarbonyl has a positive influence on cherno- and regioselectivity, but not on stereoselectivity. Thus, no asymmetric induction is observed with Co ( + )-(.S )-3-.vtx-butylpyridine in the hydroformylation of styrene23. Again no induction is observed with chiral cobalt clustersl08. Cobalt is also used in catalytic systems of the type Co(An)n(alkene)m(CO)pLq [An = coordinating or noncoordinat-ing anions, e.g., BPhJ with various chiral ligands [L = ZR4R5R6 (Z = As, N, P, Sb)]166. Low catalytic activities and inductions are observed with supported catalysts of cobalt on silica gel or alumina [in situ preparation from salt, modified with phosphanes, e.g., (+)- or (—)-Diop]89. 

L. A. Gerritsen, Hydroformylation with Supported Liquid Phase Rhodium Catalysts , Delft University Press, 1979. 

Gerritsen, L.A., Herman, J.M., Klut, W., and Scholten, J.J.F. (1980) Hydroformylation with supported liquid phase rhodimn catalysts. Part II. The location of the catalytic sites. J. Mol. Catal, 9 (2), P 157-168. 

Figure 3.6. Turn over number (TON) displayed as function of time for the hydroformylation of 1-octene using a set-up for continuous processes with SCCO2 as mobile phase and supported catalyst 2...

The rhodium complex with bis(diphenylphosphino)phenoxazine was immobilized on silica using the sol-gel technique or by a direct grafting to commercially available silica [127]. Under standard hydroformylation conditions (CO/H2 atmosphere), a neutral hydridic complex (57) and cationic species (58) (Scheme 4.35) coexist on the support and act as a hydroformylation/hydrogenation sequence catalyst, giving selectively 1-nonanol from 1-octene 98% of 1-octene were converted to mainly linear nonanal which was subsequently hydrogenated to 1-nonanol. The... 

Alumina-supported catalysts prepared using the bimetallic carbonyl precursors showed a better performance in alkene hydroformylation than conventional Co-Rh catalysts. This was related to the presence of highly dispersed Rh-Co clusters with frames corresponding to that of the parent carbonyl-precursor that were characterized by EXAFS [140, 183]. Silica-supported bimetallic entities RhCo3,... 

Both the rhodium and the cobalt complexes catalyze olefin isomerization as well as olefin hydroformylation. In the case of the rhodium(I) catalysts, the amount of isomerization decreases as the ligands are altered in the order CO > NR3 > S > PR3. When homogeneous and supported amine-rhodium complexes were compared, it was found that they both gave similar amounts of isomerization, whereas with the tertiary phosphine complexes the supported catalysts gave rather less olefin isomerization than their homogeneous counterparts (44, 45). 

Relatively few hydroformylations using supported cobalt complexes have been reported. Moffat (78, 79) showed that poly-2-vinylpyridine reversibly reacted with both Co2(CO) and HCo(CO)4, the cobalt carbonyl being displaced by excess carbon monoxide. This enabled the polymer to pick up the cobalt carbonyl at the end of the reaction and, thus, allowed it to be separated from the products by filtration. The polymer acted as a catalyst reservoir by rapidly releasing the cobalt carbonyl into solution in the presence of further carbon monoxide, so that the actual catalysis was a homogeneous process. More recently, cobalt carbonyl has been irreversibly bound to a polystyrene resin... 

Hydroformylations utilizing the polymer-supported catalysts showed comparable rates and gave nearly the same optical yield as the homogeneous analogue. Recovering of the cross-linked polymer was achieved by simple filtration with slight loss in activity but no loss in selectivity 93). 

Propylene Hydroformylation over Various Metal Carbonyl Clusters Impregnated on Metal Oxides Compared with That over Conventional Rhodium Supported Catalyst"... 

In a first approximation, the new methods correspond to the conventional solvent techniques of supported catalysts (cf Section 3.1.1.3), liquid biphasic catalysis (cf Section 3.1.1.1), and thermomorphic ( smart ) catalysts. One major difference relates to the number of reaction phases and the mass transfer between them. Owing to their miscibility with reaction gases, the use of an SCF will reduce the number of phases and potential mass transfer barriers in processes such as hydrogenation, carbonylations, oxidation, etc. For example, hydroformylation in a conventional liquid biphasic system is in fact a three-phase reaction (g/1/1), whereas it is a two-phase process (sc/1) if an SCF is used. The resulting elimination of mass transfer limitations can lead to increased reaction rates and selectiv-ities and can also facilitate continuous flow processes. Most importantly, however, the techniques summarized in Table 2 can provide entirely new solutions to catalyst immobilization which are not available with the established set of liquid solvents. 

Of particular importance for industry is the hydroformylation of alk-l-enes and one of the best processes developed so far for C2-C5 olefins employs a biphasic system in combination with a hydrosoluble rhodium complex bearing TPPTS as ligand [69-71], From this statement, Wasserscheid et al. investigated in the early 2000s the possibility of using ILs supported catalysts for this reaction [71-75], owing to the discovery by Chauvin that good linear/branched selectivities could be achieved... 

---