W.
Alsalahi
and
A. M.
Trzeciak
*
Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie St., 50-383 Wrocław, Poland. E-mail: anna.trzeciak@chem.uni.wroc.pl
First published on 1st July 2014
A new rhodium catalyst, Rh/PAA, obtained by the immobilization of Rh(acac)(CO)2 on polyacrylic acid (PAA), was successfully applied for the hydroformylation of 1-hexene in a water medium. Spectroscopic analysis evidenced that rhodium in Rh/PAA was chemically bonded to polyacrylic acid and formed a hydrido-carbonyl rhodium compound in reaction with H2/CO. Excellent results (98% conversion, TOF 1000) were obtained in the “on water” hydroformylation of 1-hexene when Rh/PAA was used together with a hydrophobic phosphine (triphenylphosphine, tri-p-tolylphosphine, or diphenyl(2-methoxyphenyl) phosphine). A similar efficiency was also obtained for a system composed of Rh(acac)(CO)2 and PPh3, tested in the same conditions in water.
Water is the most plentiful, non-environmentally harmful, nontoxic, and nonflammable solvent used by nature for biological transformations, very attractive from an economical point of view. However, water also possesses the extraordinary ability to catalyze chemical transformations between some insoluble organic reactants.2–6 Moreover, unique reactivity and selectivity is observed in water when compared with conventional organic solvents.7–10 In 1980, Rideout and Breslow discovered rate acceleration of Diels–Alder reactions between nonpolar compounds in homogeneous aqueous solutions compared with the same reactions in organic solvents.11 In 2005, Sharpless and his co-workers reported examples of organic syntheses performed in a water medium with reactants insoluble in water.9 Those reactions, termed “on water”, gave higher yields and faster kinetics than in any organic solvent. An on-water reaction is the chemical process that takes place at the organic/water phase boundary (emulsion). The formation of hydrogen bonds in interfacial water molecules at the hydrophobic interface has a free dangling hydroxyl group that protrudes into the organic phase, plays a key role in catalyzing reactions, and demonstrates an extraordinary reaction rate acceleration.9,12 Such interactions were also studied in catalytic systems for hydroformylation.13–15
In this paper, we report a new catalytic system for an on-water hydroformylation process by applying of a water-soluble immobilized catalyst, Rh/PAA, and a hydrophobic phosphine. The second system studied in the same conditions contained a water-insoluble complex, Rh(acac)(CO)2, as the rhodium source. These systems, applied for the first time in the hydroformylation of 1-hexene in water, gave very promising results. Until now there has been no detailed reports on the hydroformylation of higher olefins using the on-water methodology.
Polyacrylic acids (Mw ∼ 1800 and 450000) were purchased from Sigma-Aldrich; triphenylphosphine (PPh3) was purchased from Avocado; 1-hexene was purchased from Merck; 1-octene was purchased from Sigma-Aldrich; hydrogen (H2, 99.999%) and carbon monoxide (CO, 99.97%) were procured from Air Products. All chemicals were used without any additional purification. Distilled water was used as the reaction medium.
31P NMR (C6D6): δ 40.60 ppm (d, JRh–P = 151.75 Hz). IR: νRh–H = 2036 cm−1, νCO = 1921 cm−1.
Sample | ν CO | ν CO or νRh-H | ν CO(acac), νCO(PAA), νCH(PAA) | |||
---|---|---|---|---|---|---|
Rh(acac)(CO)2 | 2006vs, 2064vs | 1526vs, 1559s | ||||
PAA | 1714vs | 1454w | 1415w | 1269m, 1165m | ||
Rh/PAA | 2064w | 1714vs | 1455w | 1412w | 1271m, 1175m | |
Rh/PAA + H2 | 2064w | 1714vs | 1455w | 1415w | 1272m, 1177m | |
Rh/PAA + CO | 2065w | 1718s | 1457w | 1405w | 1263m, 1172m | |
Rh/PAA + H2 + CO (4h) | 2069w | 2000vw, 2100vw | 1718s | 1453w | 1413w | 1262m, 1176m |
Rh/PAA + H2 + CO (6h) | 2073w | 2006vw, 2104vw | 1711s | 1453w | 1413w | 1269m, 1176m |
Rh/PAA + H2 + CO + water | 2080m | 2023vw, 1983vw | 1713s | 1454m | 1416w | 1262m, 1171m |
Rh/PAA + H2 + benzene | 2070w | 1711vs | 1457w | 1415w | 1262m, 1172m |
The TEM analysis of Rh/PAA did not show any Rh(0) nanoparticles; however, nanoparticles appeared after reaction of Rh/PAA with H2/CO. Small, ca. 4 nm, as well as aggregated Rh(0) nanoparticles were found in different places of the TEM grids (Fig. 1). A quite different result was obtained when Rh/PAA reacted with H2/CO in water. The size of Rh(0) nanoparticles was smaller, about 2 nm.
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Fig. 1 Morphology and rhodium nanoparticle size after reaction of Rh/PAA with: (a) syngas (H2–CO), 10 bar, 80 °C and (b) syngas (H2–CO), 10 bar, 80 °C in water. |
In reactions performed without a solvent, in neat 1-hexene, only traces of aldehydes were formed. Similarly, a very low conversion of 1-hexene was noted in toluene, although PPh3 and 1-hexene are soluble in that solvent. Much better results were obtained in methanol and in a methanol–water mixture. In particular, the l/b ratio increased to a good value, 7.3. The addition of methanol to toluene resulted in a significant increase in 1-hexene conversion to aldehydes. Interestingly, when a toluene–water mixture was used, both conversion and selectivity were even better than for a toluene–methanol mixture. Such an effect was surprising because 1-hexene, Rh/PAA, and PPh3 are soluble in methanol and only Rh/PAA is soluble in water. As a rule, a faster reaction is expected in a homogeneous system than in a multiphase one. However, the most spectacular results, in respect to conversion, selectivity, and the reaction rate, were obtained in water only (Table 2). It is worth noting that the volume of water influences the reaction course only very slightly, and almost the same results were obtained using 0.5 or 1 ml of water.
Solvent | Conversion (%) | 2-Hexene (%) | Aldehydes | l/b | TOF, h−1 | |
---|---|---|---|---|---|---|
l (%) | b (%) | |||||
a Reaction conditions: 1-hexene 1.5 ml (0.012 mol), [1-hexene]/[Rh] = 800, [PPh3]/[Rh] = 13, T = 80 °C, H2–CO (1![]() ![]() |
||||||
— | 0.6 | 0.2 | 0.3 | 0.1 | ||
Toluene (1.5 ml) | 3 | 0.6 | 1.7 | 0.6 | 2.8 | |
Toluene–MeOH (1![]() ![]() |
77 | 2 | 59 | 15 | 3.9 | 296 |
Toluene–H2O (1![]() ![]() |
96 | 3 | 76 | 16 | 4.8 | 940 |
MeOH (1.5 ml)b | 92 | 4 | 72 | 11 | 6.5 | 530 |
H2O (0.5 ml) | 96 | 3 | 80 | 12 | 6.7 | 877 |
H2O (1 ml) | 97 | 3 | 79 | 14 | 5.6 | 849 |
MeOH–H2O (0.75![]() ![]() |
96 | 4 | 73 | 10 | 7.3 | 827 |
Consequently, further experiments were performed using water as the reaction medium. Such a procedure can be named “on water” because 1-hexene and PPh3 are insoluble in water. The effect of temperature on the hydroformylation of 1-hexene using the catalytic system Rh/PAA + PPh3 was studied at 50–90 °C and a constant pressure of 10 bar (Table 3). An increase in 1-hexene conversion was observed with an increase in temperature. Thus, when temperature increased from 50 to 80 °C, the yield of aldehydes increased from 21 to 94% with a decrease in the reaction time from 3 h to 1 h and a slight increase in the l/b ratio from 4.3 to 6.9. At 90 °C, the yield of aldehydes decreases to 87%, and 6% of 2-hexene, an isomerization product, was formed. Consequently, aldehyde formation was preferred at 80 °C.
T °C | P, bar | t, min | Conversion (%) | 2-Hexene (%) | Aldehydes | l/b | TOF, h−1 | |
---|---|---|---|---|---|---|---|---|
l (%) | b(%) | |||||||
a Reaction conditions: 1-hexene 1.5 ml (0.012 mol), water 1.5 ml, [Rh] (1.5 × 10−5 mol), [1-hexene]/[Rh] = 800, [PPh3]/[Rh] = 13, autoclave 50 ml. b Autoclave 100 ml, 1-hexene 3 ml, water 3 ml. | ||||||||
50 | 10 | 180 | 24 | 1 | 17 | 4 | 4.3 | 56 |
60 | 10 | 180 | 65 | 2 | 52 | 11 | 4.7 | 168 |
70 | 10 | 60 | 70 | 3 | 56 | 11 | 5.1 | 536 |
80 | 10 | 60 | 97 | 3 | 79 | 15 | 5.3 | 803 |
90 | 10 | 60 | 98 | 6 | 76 | 11 | 6.9 | 1003 |
80 | 8 | 60 | 83 | 7 | 68 | 7 | 9.7 | 677 |
80 | 6 | 60 | 62 | 6 | 53 | 3 | 17.7 | 436 |
80 | 4 | 62 | 48 | 8 | 38 | 1.7 | 22.2 | 287 |
80b | 2 | 240 | 37 | 6 | 30 | 1 | 30 | 63 |
The effect of pressure on the catalytic activity of a Rh/PAA + PPh3 system was studied at 2–10 bar and at 80 °C, and the achieved results are shown in Table 3. When the pressure of the synthesis gas decreased from 10 to 2 bar, the conversion of 1-hexene to the products decreased from 97 to 37% with a decrease in aldehyde yield from 94 to 31%. However, lowering the synthesis gas pressure caused a remarkable increase in the l/b ratio from 5.3 to 30. This is in agreement with earlier observations that a good linearity of aldehydes is favored at low pressure.1 Lower pressure favors the formation of a linear alkyl rhodium species which is next transformed to a linear acyl intermediate and finally to a normal aldehyde.
As can be deduced from the data presented on Fig. 2, the effect of temperature on hydroformylation selectivity is rather small. For instance, the l/b value changed from 4.3 to 6.9 when the temperature rose from 50 to 90 °C. In contrast, the pressure has a decisive effect on the yield of aldehydes as well as on hydroformylation selectivity. At 4 bar, the l/b ratio was 22.2, and at 2 bar, it reached 30.
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Fig. 2 Graphs depicting the influence of 1![]() ![]() |
The effect of the [PPh3]/[Rh] ratio on the reaction course was studied in the range from 0 to 13 at 80 °C at 10 bar. The results presented in Table 4 show that in the absence of phosphine Rh/PAA catalyzes only the isomerization of 1-hexene to 2-hexene. However, already a 5-fold excess of PPh3 made it possible to get 57% of aldehydes. With an increase in the [PPh3]/[Rh] ratio, the conversion of 1-hexene increased to 92% together with an increase in the l/b ratio to 5.7. Interestingly, high catalytic activity and good selectivity towards aldehydes were also obtained with the application of other water-insoluble phosphines, namely tri-p-tolylphosphine and diphenyl(2-methoxyphenyl) phosphine with Rh/PAA (Table 4). However, it should be noted that the kind of phosphine has a remarkable influence on the TOF values, and the highest TOF was obtained for PPh3.
Entry | [L]/[Rh] | Time (min) | Conversion (%) | 2-Hexene (%) | Aldehydes | l/b | TOF, h−1 | |
---|---|---|---|---|---|---|---|---|
l (%) | b (%) | |||||||
a L = PPh3.
b L = tri-p-tolylphosphine.
c L = diphenyl(2-methoxyphenyl)phosphine.
d Reaction conditions: 1-hexene 1 ml (0.008 mol), water 1 ml, [Rh] 1 × 10−5 mol, [1-hexene]/[Rh] = 800, 80 °C, H2–CO(1![]() ![]() |
||||||||
1a | 0 | 240 | 8 | 8 | ||||
2a | 5 | 240 | 62 | 5 | 44 | 13 | 3.4 | 86 |
3a | 10 | 174 | 90 | 4 | 70 | 16 | 4.4 | 382 |
4a | 13 | 120 | 92 | 4 | 88 | 15 | 5.7 | 718 |
5b | 13 | 120 | 90 | 4 | 66 | 20 | 3.2 | 538 |
6c | 13 | 120 | 85 | 2 | 62 | 20 | 3.1 | 344 |
The hydroformylation of 1-hexene was also performed with another Rh/PAA catalyst containing polyacrylic acid, Mw = 450000. The rhodium content in this catalyst was significantly lower than in Rh/PAA immobilized on a polymer of Mw = 1800. Nevertheless, this catalysts also gave quite good results, 97% of aldehydes with l/b = 4.6 after 150 min.
In order to recognize the possibility of the in situ formation of an Rh/PAA catalyst, Rh(acac)(CO)2 and PPh3 were used in the next experiment together with PAA added to the reaction mixture. The reaction was even faster than with Rh/PAA; however, a similar yield of the products was obtained. Next, Rh(acac)(CO)2 was used with PPh3 only, without PAA, and, surprisingly, the catalytic result was very promising (Table 5). The final composition of the products was similar to that obtained with Rh/PAA, but the TOF values were higher. At a lower pressure, 4 or 6 bar, l/b increased to attractive values, 16 and 21. Interestingly, the hydrophobic complex HRh(CO)(PPh3)3 can also be successfully applied for the hydroformylation of 1-hexene in water giving the highest TOF, 1903 h−1, noted in these studies.
Catalyst precursor | P bar | t min | Conversion (%) | 2-Hexene (%) | Aldehydes | l/b | TOF, h−1 | |
---|---|---|---|---|---|---|---|---|
l (%) | b (%) | |||||||
a Reaction conditions: a,d 1-hexene 1 ml (0.008 mol), water 1 ml, autoclave 35 ml, b,c 1-hexene 1.5 ml (0.012 mol), water 1.5 ml, autoclave 50 ml, a,b,c [1-hexene]/[Rh] = 800, [PPh3]/[Rh] = 13, d [1-hexene]/[Rh] = 420, [PPh3]/[Rh] = 6.8. T = 80 °C. | ||||||||
Rh/PAA (Mw ∼ 450![]() |
10 | 150 | 97 | 5 | 74 | 16 | 4.6 | 495 |
Rh(acac)(CO)2b | 10 | 40 | 97 | 11 | 77 | 5 | 15.4 | 1658 |
Rh(acac)(CO)2b | 6 | 40 | 76 | 18 | 51 | 2 | 25.2 | 967 |
Rh(acac)(CO)2b | 4 | 40 | 62 | 20 | 37 | 1 | 37 | 574 |
Rh(acac)(CO)2d | 10 | 65 | 99 | 4 | 78 | 16 | 4.9 | 1153 |
Rh(acac)(CO)2d | 6 | 70 | 73.2 | 13 | 56.7 | 3.5 | 16 | 967 |
Rh(acac)(CO)2d | 4 | 75 | 55.4 | 16.1 | 37.5 | 1.8 | 21 | 374 |
HRh(CO)(PPh3)3c | 10 | 60 | 98 | 8 | 82 | 6 | 13.7 | 1903 |
Fig. 3 shows the H2/CO pressure drop during the hydroformylation of 1-hexene catalyzed by Rh/PAA, Rh(acac)(CO)2, and HRh(CO)(PPh3)3. As the last two systems are totally hydrophobic, the name “on water” is suitable for their description.
With these improved reaction conditions in hand, we decided to investigate the on-water hydroformylation of other alkenes. 1-Octene showed good conversion, 98% (Table 6, entry 1). The on-water hydroformylation reaction using 2-hexene and styrene as the substrates gave 76% and 67.0% conversion and 76% and 64% aldehyde selectivity. However, the l/b ratio was expectedly poor, 0.07 and 0.7, respectively (Table 6).
Substrate | t, min | Conv.a (%) | Aldehydes | l/b | TOF, h−1 | |
---|---|---|---|---|---|---|
l (%) | b (%) | |||||
a Rh(acac)(CO)2 as catalyst, [1-hexene]/[Rh] = 420, [PPh3]/[Rh] = 6.5, p = 1 bar.
b Reaction conditions: Substrate 1.5 ml, water 1.5 ml, [sub]/[Rh] = 800, L = PPh3 [PPh3]/[Rh] = 13, T = 80 °C, P(H2–CO) = 1![]() ![]() |
||||||
1-Octene | 120 | 98 | 77 | 13 | 5.9 | 760 |
2-Hexene | 180 | 76 | 5 | 71 | 0.07 | 216 |
Styrene | 90 | 67 | 26 | 38 | 0.7 | 389 |
Substrate | Time min | Conversion (%) | 2-Hexene (%) | Aldehydes % | l/b | TOF, h−1 |
---|---|---|---|---|---|---|
a Reaction conditions: [sub]/[Rh] = 800, L is PPh3 [PPh3]/[Rh] = 13, T = 80 °C, p(H2–CO) = 1![]() ![]() |
||||||
1-Hexene | 70 | 95.7 | 4.8 | 90.9 | 6.5 | 752 |
120 | 95.6 | 4.1 | 90.1 | 6.7 | 751 | |
180 | 96.3 | 4.5 | 91.1 | 8.1 | 306 | |
1-Octene | 120 | 97.7 | 3.7 | 92.4 | 3.8 | |
120 | 77 | 2.4 | 70.9 | 4.1 | ||
120 | 95.2 | 2.2 | 91.4 | 3.9 |
In reaction with 1-octene as the substrate, only the water phase was used for the first recycling producing 70.9% of aldehydes. For the next run, all rhodium was used again, according to the procedure described for 1-hexene.
For a better understanding of rhodium transformations in the studied system, the reaction of Rh(acac)(CO)2 with PPh3 and H2 (1 bar) was performed in water. It should be mentioned that PPh3 reacts with Rh(acac)(CO)2 in any organic solvent producing Rh(acac)(CO)(PPh3), which in the presence of a PPh3 excess and H2/CO forms a catalytically active hydrido-carbonyl species. Reaction with H2/CO takes place only under elevated pressure, and no reaction was observed at atmospheric pressure in benzene or toluene. In contrast, formation of HRh(CO)(PPh3)3 was observed in the presence of methanol or isopropanol. Unexpectedly, when a suspension of Rh(acac)(CO)2 and PPh3 in water was treated with H2 (1 bar), the complex HRh(CO)(PPh3)3 was formed in a stoichiometric amount (Scheme 2).
Such a synthetic procedure differs remarkably from those reported in the literature.18–20 The most efficient syntheses of HRh(CO)(PPh3)3 apply KOH, NaBH4, or hydrazine in an ethanol solution.18
The presented systems can be used for any higher olefin, as was demonstrated for 1-hexene, 2-hexene, and 1-octene.
Recycling experiments showed that a rhodium catalyst can be recovered without a loss of its catalytic activity. However, during hydroformylation rhodium is leached to the organic phase, which complicates the efficient separation of aldehydes from the catalyst. We are now working on the improvement of this step and preliminary results show that after the catalytic cycle rhodium can be transferred back to the water phase.
Explanation of the high catalytic activity of the presented “on water” system can only in part be based on specific interactions between the reactants, similarly as it was described in the literature. In our opinion, reactions of the rhodium precursor with H2/CO are remarkably influenced by the presence of water, which is not only a solvent but also a reactant. As was shown, in a water medium, a catalytically active HRh(CO)(PPh3)3 complex was formed in high yield under very mild conditions as a result of efficient H2 activation. Such activation was realized without any additives, in particular in the absence of a base that could eventually facilitate heterolytic splitting of H2.
In conclusion it should be pointed out that in the presented catalytic systems water plays not only the role of a reaction medium but it is also involved in the chemical transformations of rhodium complexes to catalytically active forms. A combination of these two functions results in the creation of a very active, simple, and environmentally friendly catalytic system for the hydroformylation of higher olefins.
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