Novel α-fluorinated cyclic phosphite and phosphinite ligands and their Rh-complexes as suitable catalysts in hydroformylation

Odinets, Irina L.; Kégl, Tamás; Шарова, Е. В.; Аrtyushin, О. I.; Goryunov, E. I.; Molchanova, G. N.; Mastryukova, T. A.; Röschenthaler, Gerd Volker; Keglevich, György; Kollár, László

doi:10.1016/j.jorganchem.2005.04.038

Cited by 9 publications

(1 citation statement)

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“…A highly regioselective catalyst not in the Klosin and Landis study is the Rh(I) complex of 3 (Figure ), developed by Diéguez et al − This catalyst exhibits excellent regioselectivity for the iso product of styrene (37.5 iso/n ) at 20 °C and 10 atm; however the turnover frequency (TOF) is only 15, corresponding to a pseudo-first-order rate constant of 4.2 × 10 −6 s −1 . Finally, the Rh(I) complex of the monophosphite ligand 6 developed by Odinets et al, which is also not in the Klosin and Landis study, exhibits a high regioselectivity (22.8 iso/n ) at 40 °C and 100 atm, but the activity of the catalyst is low, with an initial TOF of 55, corresponding to a rate constant of about 3.8 × 10 −6 s −1 . When the reaction temperature is raised to 100 °C, the initial TOF increases to 2000 ( k = 1.4 × 10 −4 s −1 ), which is comparable to that of the Rh(I) complex of 8 , but the regioselectivity decreases to 1.3 iso/n , which is significantly lower than that of the Rh(I) complex of 8 .…”

Section: Resultsmentioning

confidence: 99%

Study of the Effects of Alkali Metal Salts on Styrene Hydroformylation Reactions Catalyzed by Rhodium(I) Complexes of Bis(phosphite) Ligands

Owens

Gray

2008

Organometallics

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A functionalized R,ω-bis(phosphite-donor) ligand containing two amido groups, 8, has been prepared from tartaric acid. An in situ formed rhodium(I) metallacrown ether complex of 8 has been compared to an in situ formed rhodium(I) complex of (R,R)-Chiraphite for the hydroformylation of styrene. Both Rh(I) complexes are active catalysts, but the complex of (R,R)-Chiraphite exhibits a higher regioselectivity than does the metallacrown ether catalyst (iso/n of 10.1 versus 3.9) as expected. The additions of alkali metal salts to the hydroformylation reactions cause increases in the regioselectivities (approximately 2-fold for both LiBPh 4 • 3dme and NaBPh 4 for ligand 8; 3-fold for both LiBPh 4 • 3dme and NaBPh 4 for (R,R)-Chiraphite) with virtually no effect on the activity. The facts that (1) no change in the iso/n ratio is observed upon addition of the noncoordinating salt, TBA • BPh 4 , (2) LiBPh 4 • 3dme has little effect on the regioselectivity of an in situ formed rhodium(I) complex of diphos, and (3) the increase in regioselectivity levels out at high salt:Rh ratios suggest the increase in regioselectivity is due to coordination of the alkali metal salt to the oxygen of a carbonyl ligand and to the phosphite oxygens during the regioselectivity-determining step. This proposal is consistent with the observation of only weak 1:1 coordination of LiBPh 4 • 3dme with a model metallacrown ether, cis-Mo(CO) 4 (8) in acetonitrile-d 3 .

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Section: Resultsmentioning

confidence: 99%

Study of the Effects of Alkali Metal Salts on Styrene Hydroformylation Reactions Catalyzed by Rhodium(I) Complexes of Bis(phosphite) Ligands

Owens

Gray

2008

Organometallics

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Design and Synthesis of Phosphite Ligands for Homogeneous Catalysis

Gual

Godard

Fuente

et al. 2012

Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis

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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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Novel α-fluorinated cyclic phosphite and phosphinite ligands and their Rh-complexes as suitable catalysts in hydroformylation

Cited by 9 publications

References 39 publications

Study of the Effects of Alkali Metal Salts on Styrene Hydroformylation Reactions Catalyzed by Rhodium(I) Complexes of Bis(phosphite) Ligands

Study of the Effects of Alkali Metal Salts on Styrene Hydroformylation Reactions Catalyzed by Rhodium(I) Complexes of Bis(phosphite) Ligands

Design and Synthesis of Phosphite Ligands for Homogeneous Catalysis

Carbonylation of Alkenes and Dienes

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