Homogeneous Catalysis

94 HYDROFORMYLATION

Hydroformylation of propylene is carried out in water. The solubility of propylene in water is sufficiently high to give an acceptable rate. The use of a buffer component such as Na2HPO4 has been suggested for the control of pH. However, the use of such salts has been shown to have definite influence on the reaction rate as well as product selectivity. The aldehyde product forms an organic layer, which is easily separated by decantation from the catalystcontaining aqueous phase. The high efficiency of the recovery process ensures that Rh losses are in parts per billion ranges. Ruhrchemie/Rhone-Poulenc reports that over a period of 10 years, for the production of 2 million tons of n- butyraldehyde, the loss of rhodium has been approximately 2 kg.

The successful commercial use of TPPTS has triggered much research for other water-soluble phosphines. While some of these certainly give highly active and selective catalytic systems, as yet their cost of manufacturing make them commercially unattractive. For example, the bis-phosphine 5.14 gives a catalytic system that is about ten times more active than the one with TPPTS and also shows a higher selectivity ( 98%) towards n-butyraldehyde. Its synthesis, however, is a five-step process and involves expensive reagents.

Recently Union Carbide has reported a separation technique that utilizes monosulfonated triphenyl phosphine (TPPMS). This technique may be useful for the hydroformylation of high molecular weight and less volatile alkenes such as octene, dodecene, and styrene. These alkenes are much less soluble in water than propylene. This means that with the Rh-TPPTS catalytic system in water, unacceptably low rates of hydroformylation are obtained. The use of solubilizing agents such as N-methylpyrrolidone, polyalkylene glycols, etc. makes alkali metal salts of TPPMS soluble in nonpolar organic phase. This probably is due to the formation of reverse micelles, aided by the solubilizing agents. Rhodium complexes of TPPMS can be used to hydroformylate higher olefins in such an organic medium. At the end of the reaction the single phase is separated into a nonpolar and a polar phase by the addition of water or methanol, or by a change in temperature. The catalyst remains in the polar phase, while the product goes into the nonpolar phase.

Another novel technique for separation of the TPPTS-based catalyst is by immobilizing it on a solid support. This catalyst consists of a thin film of an aqueous solution of rhodium–TPPTS complex supported on high-surface-area

silica. The substrate alkene is then hydroformylated in an organic solvent such as cyclohexane, which is immiscible with water. The catalytic reaction presumably takes place at the aqueous–organic interface. However, the commercial viability of the Union Carbide discovery and the solid-supported aqueous-phase catalyst remain to be established on an industrial scale.

5.2.6Catalyst and Ligand Degradation

The lifetime of the rhodium precatalyst depends on the rate at which the metal complex HRh(CO)(TPPTS)3 and the excess ligand TPPTS undergo decomposition. The catalyst lifetime is considerably increased by occasional addition of extra ligand. In general an increase in the reaction temperature and/or CO pressure results in a decrease in the catalyst lifetime.

With 5.1 as the precatalyst, the degradation products in the propylene hydroformylation reaction are diphenylpropyl phosphine (Ph2PC3H7), benzene, and less soluble rhodium complexes. These complexes are tentatively formulated as phosphido clusters. Formation of all the products could be rationalized by the hypothetical catalytic cycle shown in Fig. 5.6.

Figure 5.6 Catalytic cycle for the degradation of PPh3. Only four coordination sites around Rh are shown. In some of the hypothetical intermediates Rh may be five or six coordinated.

96 HYDROFORMYLATION

The basic assumption is the intramolecular oxidative addition of PPh3 in the coordinatively unsaturated intermediate 5.15 to give the phosphido complex 5.16. This reacts with propylene to give 5.17, which undergoes reductive elimination to give Ph2PC3H7 and the phenyl complex 5.18. The latter undergoes oxidative addition of dihydrogen to give 5.19. This in turn eliminates benzene reductively and regenerates 5.15. The vacant coordination sites of 5.15 and 5.18 are, of course, normally occupied by ligands such as PPh3 or CO. Consequently, the rate of degradation in the presence of excess ligand would be very small.

5.3COBALT-BASED HYDROFORMYLATION

The catalytic cycle for the cobalt-based hydroformylation is shown in Fig. 5.7. Most cobalt salts under the reaction conditions of hydroformylation are converted into an equilibrium mixture of Co2(CO)8 and HCo(CO)4. The latter undergoes CO dissociation to give 5.20, a catalytically active 16-electron intermediate. Propylene coordination followed by olefin insertion into the metal– hydrogen bond in a Markovnikov or anti-Markovnikov fashion gives the branched or the linear metal alkyl complex 5.24 or 5.22, respectively. These

Figure 5.7 Catalytic cycle for the hydroformylation of propylene with cobalt catalyst. The inner and outer cycles show the formation of linear and branched isomers.

complexes can undergo CO insertion into the metal–alkyl bonds to give 5.25 and 5.23, respectively. The product aldehydes are generated from these species by reaction with both dihydrogen and HCo(CO)4. Under the catalytic conditions the latter reaction is insignificant compared to the former.

The cobalt and rhodium catalysts have one important difference between their respective mechanisms. Unlike in the rhodium-catalyzed process, there is no oxidative addition or reductive elimination step in the cobalt-catalyzed hydroformylation reaction. This is reminiscent of the mechanistic difference between rhodiumand cobalt-based carbonylation reactions (see Section 4.2.3). The basic mechanism is well established on the basis of in situ IR spectroscopy, kinetic and theoretical analysis of individual reaction steps, and structural characterization of model complexes.

Both Co(CO)4(COPrn) and Co(CO)4(COPri) have been isolated, and their reactions with H2 as well as HCo(CO)4 have been studied. On the basis of such studies participation by intermediates such as 5.23 and 5.25 in the catalytic cycle is firmly established. The reactions of HCo(CO)4 with Co(CO)4(COPri) and Co(CO)4(COPrn) are about 20–30 times faster than the corresponding reactions with dihydrogen at 25 C. However, as already mentioned, at high temperature (>100 C) and pressure (>100 bar), reaction with dihydrogen is the main product-forming step.

For the other catalytic intermediates, there are spectroscopic data and/or strong theoretical arguments in favor of their existence. Thus Co(CO)3(COMe), an analogue of 5.23 and 5.25 has actually been observed spectroscopically at low temperature by the matrix isolation technique. A similar experimental technique has also established the formation of Co(CO)3(Me), an analogue of 5.22 and 5.24.

In the Shell process (SHOP) phosphine-modified cobalt-catalyzed hydroformylation is one of the steps in the synthesis of linear alcohols with 12–15 carbon atoms (see Section 7.4.1). Two important characteristics of this reaction should be noted. First, the phosphine-modified precatalyst HCo(CO)3(PBun3) is less active for hydroformylation than HCo(CO)4 but more active for the subsequent hydrogenation of the aldehyde. In this catalytic system both hydroformylation and hydrogenation of the aldehyde are catalyzed by the same catalytic species. Second, the phosphorus ligand-substituted derivatives are more stable than their carbonyl analogues at higher temperatures and lower pressures (see Table 5.1).

In situ IR spectroscopic studies have been carried out on the CO2(CO)8 plus PBun3 –based catalytic system with ethylene or n-octene as the olefins. Unlike in the case of Co2(CO)8, where HCo(CO)4 and Co(CO)4(COR) may be observed, in the presence of PBun3, no Co(CO)3(PBun3)(COR) or Co(CO)3(PBun3))(R) types of complexes could be seen. This presumably is because of low concentrations of such intermediates under operating conditions. The mechanism of hydroformylation is assumed to be similar to the one shown in Fig. 5.7. Very little direct mechanistic evidence at a molecular level is available on the aldehyde hydrogenation reaction.

98 HYDROFORMYLATION

5.4OTHER HYDROFORMYLATION REACTIONS

Apart from the processes discussed so far, there are other industrial and patented processes where hydroformylation reactions are employed. A few selected ones are summarized in Table 5.2.

TABLE 5.2 Hydroformylation Reaction Processes

100 HYDROFORMYLATION

3.Suggest an isotope-labeling experiment for characterization of the catalytic intermediate, observed by in situ IR in the hydroformylation of ethylene by cobalt carbonyl.

Ans. HCo(CO)4 is the only species observed. On deuterium labeling a shift in the IR of Co-H(D) by a factor of about 1.44.

4.Treatment of RhClL3 with CH3CHO gives a complex with IR bands at 1615 and 1920 cm 1, and a high-field twelve-line 1H NMR signal. This complex on heating gives RhClL3 and CH3CHO back only if the latter is removed as it is formed. Explain these observations. In what way are they relevant to the catalytic cycle of Fig. 5.1?

Ans. Oxidative addition to give 5.13. The Rh–H and the acyl group absorb at 1920 and 1615 cm 1. Rh-H in NMR is coupled to three inequivalent 31P and 103Rh nuclei. Thermodynamically reductive elimination is not a favored reaction. The complex is a model for 5.7 (see D. Milstein, J. Am. Chem. Soc., 104, 5227–28, 1982).

5.In ethylene hydroformylation with RhH(CO)(PPh3)3, after several hours of reaction a material containing C, H, and P is isolated that has NMR signals at 1H (31P) 7.0 and a triplet and quartet between 0 and 3 . What is the material, and how is it formed?

Ans. Ph2PC2H5. Degradation of the catalyst by a cycle similar to that of Fig. 5.6.

6.What are the mechanisms of 5.1-catalyzed isomerizations of 2-hexene to 3-hexene, and 1-methyl cyclohexene to 1-methylene cyclohexane? Suggest an experiment.

Ans. For both, insertion followed by -elimination. For 1-methyl cyclohexene insertion in a Markovnikov manner, while for 2-hexene anti-Markovni- kov and Markovnikov are indistinguishable. A D label on the methyl of 1-methyl cyclohexene should result in D scrambling of the 1,2,6 positions of 1-methylene cyclohexane.

7.Assuming that only the reactions shown in Fig. 5.1 operate for the hydroformylation of propylene to n-butyraldehyde with 5.1 as the catalyst, and oxidative addition of dihydrogen is the rate-determining step, what should be the rate expression? What is the implicit assumption?

Ans. Rate expression as in 5.6 with a = b = 1 and L instead of CO in the denominator. Assumption: 5.1 CO C3H6 ` 5.6 L.

8.What qualitative features do you expect in the 1H NMR spectra of 5.8, 5.9, and 5.10 at room and low temperatures?

Ans. At room temperature all three complexes in rapid equilibrium and one broad signal. At low temperatures: 5.8: 1H coupled to 103Rh and two

BIBLIOGRAPHY 103

For TPPMS-based Union Carbide work, see Chem. Eng. News, April 17, 1995, p. 25.

For more general articles, see D. M. Roundhill, in Advances in Organometallic Chemistry, ed. by F. G. A. Stone and R. West, Academic Press, Vol. 38, 1995, pp. 155– 88.

B.Driessen-Holscher, in Advances in Catalysis, ed. by D. D. Eley, W. O. Hagg, B. Gates, and H. Knozinger, Academic Press, New York, Vol. 42, 1998, pp. 473–506.

Section 5.2.6

A. G. Abatjoglou et al., Organometallics, 3, 923–26, 1984.

Sections 5.3 and 5.4

See articles listed under 5.1 to 5.2.4.

Section 5.5

B.Cornils and E. Wiebus, Chem. Tech. (Jan. 1995) 33; Kirk and Othmer Encyclopedia of Chemical Technology, 4th edn, John Wiley & Sons, New York, Vol. 16, 1992, pp. 640–51.