Aqueous biphasic hydroformylation catalyzed by rhodium carbonyl complexes modified with bioligands

Paganelli, Stefano; Marchetti, Mauro; Bianchin, M; Bertucci, Carlo

doi:10.1016/j.molcata.2007.01.027

Cited by 20 publications

(18 citation statements)

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“…In this context, some years ago we reported highly efficient and chemoselective hydroformylation [10][11][12] and hydrogenation [8] reactions using water-soluble complexes derived from the interaction between Rh(CO) 2 (acac) or [Ir(COD)Cl] 2 , respectively, with human serum albumin (HSA). Previous studies, carried out by us on the catalytic system Rh/HSA, showed an outstanding correspondence between the surface distribution of Rh and S atoms of the protein, therefore we hypothesized that the metal atom mainly interacts with the sulphur atoms [13,14]: the great affinity of "soft" metals, such as rhodium, for the thiolic group is well known [15]. As a matter of fact many rhodium complexes modified with thioligands have been successfully employed in catalytic reactions in homogeneous phase in organic solvents [16][17][18][19][20][21][22][23].…”

Section: Introductionmentioning

confidence: 86%

“…As a matter of fact many rhodium complexes modified with thioligands have been successfully employed in catalytic reactions in homogeneous phase in organic solvents [16][17][18][19][20][21][22][23]. Our goal was to study catalytic processes in the presence of water-soluble sulphur containing ligands: in particular we used some thio-oligopeptides as ligands in the rhodium catalyzed hydroformylation of styrene [14]. More recently, we turned our attention to simple and cheap water-soluble low molecular weight thioligands such as the aminoacid (l)-Cysteine and [(S)-1-[(S)-3-mercapto-2-methylpropanoyl]pyrrolidine-2-carboxylic acid] (sold as a pharmacologically active ACE inhibitor, named Captopril ® ).…”

Section: Introductionmentioning

confidence: 99%

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Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Paganelli

Piccolo²,

Pontini

et al. 2015

Catalysis Today

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a b s t r a c tRh(DHTANa) is a new water-soluble catalyst easily obtained by mixing in water the catalytic precursor [Rh(COD)Cl] 2 and the dihydrothioctic acid sodium salt (DHTANa). This catalyst showed to be very active in the hydrogenation of unsaturated substrates as 2-cyclohexen-1-one, the biomass-derived furfural and acetophenone. In this last case the catalytic system obtained by using as water-soluble ligand (R)-(DHTANa) afforded (R)-1-phenylethanol with very modest enantioselectivity. Rh(DHTANa) was active also in the aqueous biphase hydroformylation of styrene producing exclusively the two corresponding aldehydes with 80-86% selectivity toward the branched aldehyde 2-phenylpropanal. This new catalytic system was easily recycled in both hydrogenation and hydroformylation processes and no leaching phenomenon was observed.

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Section: Introductionmentioning

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Paganelli

Piccolo²,

Pontini

et al. 2015

Catalysis Today

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“…The major crystalline phase in the as prepared catalyst is ascribed to struvite, i.e. MgNH 4 PO 4 · (H 2 O) 6 , JCPDS card no. 71-2089 (a).…”

Section: Resultsmentioning

confidence: 99%

“…The struvite simulated PXRD pattern (FWHM = 0.3°) well reproduces the major peaks. Some peaks, marked with asterisks, are not ascribed to MgNH 4 PO 4 · (H 2 O) 6 but could be related to the presence of a mixture of minor crystalline phases of sodium phosphate and sodium hydrogen phosphate hydrate or to the presence of organic phosphates. After the catalytic process Rh-EPS PXRD pattern changes considerably.…”

Section: Resultsmentioning

confidence: 99%

“…In particular, the use of environmentally more benign solvents as water has been developed [2,3] and the hydroformylation process represents one of the most striking examples of this catalytic methodology [1][2][3][4]. The use of natural compounds, such as aminoacids, peptides, proteins and sugars as ligands to maintain metallic species soluble and active in aqueous biphasic systems was deeply investigated [5][6][7][8][9][10][11][12][13][14][15]. Since bacterial cells may often synthesize and secret polysaccharides [16], recently we envisaged a new way of using bacteria to produce carbohydrates able to bind metals during their growing in the presence of suitable metal salts.…”

Section: Introductionmentioning

confidence: 99%

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A new biogenerated Rh-based catalyst for aqueous biphasic hydroformylation

Paganelli

Piccolo²,

Baldi

et al. 2015

Catalysis Communications

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A new bio-generated rhodium based system embedded in a peculiar polysaccharide matrix (Rh-EPS), was obtained and purified from cultures of bacterial cells of Klebsiella oxytoca DSM 29614. The product was analyzed with different techniques to obtain information on its structure-property correlation. In order to determine its catalytic activity and selectivity in the aqueous biphasic hydroformylation some olefins were chosen as model substrates, obtaining fine-good results.

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Carbonylation of Alkenes and Dienes

Kégl

2008

Modern Carbonylation Methods

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In the beginning, only cobalt catalysts were utilized for hydroformylation under relatively vigorous conditions. The moderate selectivity of the generally more desired linear isomers, the substantial formation of by-products, and the low stability of the catalysts forced more appropriate catalytic systems to be developed. Using donor ligands such as phosphanes resulted in an increase in the linear selectivity. Rhodium-containing catalysts, however, permitted the use of much milder conditions in combination with suitable ligands. Other transition metals such as ruthenium, palladium, platinum, and iridium also tended to show activity for hydroformylation, albeit a vast majority of works on hydroformylation still concentrated on rhodium-containing systems. Cobalt CatalystsThe initial rate of Co 2 (CO) 8 -catalyzed cyclohexene hydroformylation, triethyl orthoformate carbonylation, and CoH(CO) 4 formation from Co 2 (CO) 8 and H 2 is reduced by the addition of dinitrogen, argon, or xenon. It is assumed that the additional gas competes with one or more reactants for a coordinatively unsaturated site responsible for their activation, thus affecting the reaction rate [1].The carbonylation reaction of propylene oxide in the presence of various [Lewis acid] þ [Co(CO) 4 ] À salts was investigated using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. b-Alkoxy-acyl-cobalttetracarbonyl species were found to be key intermediates from which two reaction routes start depending on the applied Lewis acid. Labile Lewis acid-alkoxy combinations primarily favor the production of lactone products [2].The reaction of olefins (1-octene, 3,3-dimethylbutene, cyclohexene) introduced into a preequilibrated Co 2 (CO) 8 þ H 2 system was investigated by high-pressure infrared spectroscopy. Based on the observed induction period for the formation of the corresponding aldehyde, the decrease in HCo(CO) 4 concentration and increase in Co 2 (CO) 8 concentration during the induction period, the active catalytic species of the type H x Co y (CO) z was proposed [3]. Experiments with isotope mixtures of H 2 /D 2 in the gas phase during the various steps of the reaction showed that the ratio of H/D isotopes in the hydrocarbon portion of the aldehyde product correlates with the HCo(CO) 4 /DCo(CO) 4 ratio in solution, whereas the RC(¼O)H/RC(¼O)D product ratio correlates with the H 2 /D 2 in the gas phase. It was concluded that the dominant pathway for the hydrogenolysis step in this type of hydroformylation is the direct reaction of hydrogen or deuterium with the acyl complex intermediate [4].The effect of argon (280 bar) on the rate of aldehyde formation in 1-hexene hydroformylation catalyzed by Co 2 (CO) 8 at 50 C, 70 bar P(CO) and 85 bar P(H 2 ) in toluene was investigated by high-pressure FT-IR spectroscopy. The initial rate of the reaction was found to be reduced by the presence of argon. A similar effect was observed in the RhH(CO)(PPh 3 ) 3 -catalyzed cyclohexene hydroformylation reaction [5]. 162j 7 Carbonylation of Alkenes and D...

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Aqueous biphasic hydroformylation catalyzed by rhodium carbonyl complexes modified with bioligands

Cited by 20 publications

References 17 publications

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

A new biogenerated Rh-based catalyst for aqueous biphasic hydroformylation

Carbonylation of Alkenes and Dienes

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