Reactions of Rh(acac)[P(OPh)3]2 with H2, CO and olefins

Trezeciak, A.M.; Ziółkowski, Józef J.; Aygen, S.; Eldik, Rudi van

doi:10.1016/0304-5102(86)87012-2

Cited by 37 publications

(12 citation statements)

References 9 publications

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“…The highest rates were observed at the P/Rh ratio of three. Similar observations were reported by Ziolkowski and co‐workers who observed a rate depletion at P(OPh) 3 : Rh ratios > 2:1 for hexene hydroformylation 36‐39 . In case of the triphenyl phosphite ligand promoted reaction, the active species is either HRh(acac)(CO)[P(OPh) 3 ] 2 or HRh(CO)[P(OPh) 3 ] 3 depending on the reaction condition, concentrations, and gas composition 35,36 .…”

Section: Resultssupporting

confidence: 84%

“…The results in Figure 5 show a linear dependence on the catalyst concentration, indicating a first‐order kinetics. A first‐order dependence is expected from the mechanism proposed by Trzeciak and Ziolkowski as shown in Figure 6 35–39 . An increase in the [Rh(CO) 2 (acac)] concentration would lead to an increase in the active catalyst concentration and thus an increase in the reaction rate.…”

Section: Resultsmentioning

confidence: 82%

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Kinetics of hydroformylation of camphene using rhodium‐phosphite catalyst

Pagar

Rajurkar

Deshpande

2020

Int J of Chemical Kinetics

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Kinetics of hydroformylation of camphene was investigated in the presence of [Rh(CO) 2 (acac)]/P(OPh) 3 catalyst in a temperature range of 363-383 K. The influence of parameters such as stirring speed, camphene, catalyst, ligand concentrations, and partial pressures of H 2 and CO on the activity and selectivity of the catalyst has been studied. The rate showed a first-order dependence with respect to catalyst and camphene concentrations. The effect of partial pressure of hydrogen showed fractional order dependence. The plots of rate versus excess ligand, that is, (P(OPh) 3 ) concentration and rate versus CO partial pressure passed through maxima and showed typical substrate/ligand inhibited kinetics. An empirical rate equation has been proposed and found to be in good agreement with the observed rate data. The kinetic parameters and activation energy were also evaluated. K E Y W O R D Scamphene, homogeneous, hydroformylation, kinetics, rhodium-phosphite Int J Chem Kinet. 2020;52:485-495.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 82%

Kinetics of hydroformylation of camphene using rhodium‐phosphite catalyst

Pagar

Rajurkar

Deshpande

2020

Int J of Chemical Kinetics

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“…After further addition of 2.5 atm of CO (5 atm total pressure) and heating of the system at 80°C for 1 h, the doublet signal in the 31 P{ 1 H} NMR spectrum at δ = 157.9 ppm, the multiplet signal at δ = 80 ppm and the hydride signal at δ = -11. . [20] We assigned the major doublet signal at δ = 158.9 ppm in the 31 . [20] The minor signal at δ = 154.6 (J Rh,P = 194.6 Hz) ppm is attributed to the dicarbonyl species [RhH(CO) 2 (1) 2 ] (12), whose hydride signal is not detected in the 1 H NMR spectrum due to its low concentration.…”

Section: Reactivity Of [Rh(acac)(co) 2 ]/1-3 With Co and Hmentioning

confidence: 99%

“…[20] We assigned the major doublet signal at δ = 158.9 ppm in the 31 . [20] The minor signal at δ = 154.6 (J Rh,P = 194.6 Hz) ppm is attributed to the dicarbonyl species [RhH(CO) 2 (1) 2 ] (12), whose hydride signal is not detected in the 1 H NMR spectrum due to its low concentration. The signals at δ = 140.8 and 70.2 ppm could correspond to mixed complexes with phosphite/phosphonate and carbon monoxide ligands formed by the partially decomposed ligand.…”

Section: Reactivity Of [Rh(acac)(co) 2 ]/1-3 With Co and Hmentioning

confidence: 99%

New Ligands for Rh‐Catalysed Hydroformylation of 1‐Octene in Supercritical Carbon Dioxide – X‐ray Structure of [Rh{PPh₂(OC₉H₁₉)}₄]PF₆

et al. 2006

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The new P‐donor ligands PPh3–n(OC9H19)n (n = 3, 2, 1) containing branched alkyl chains were synthesised and their coordination to RhI and PdII studied. The X‐ray structure of [Rh{PPh2(OC9H19)}4]PF6 was determined. Reaction of the [Rh(acac)(CO)2]/PPh3–n(OC9H19)n systems with CO/H2 at 5 atm and 80 °C in toluene led to the formation of [RhH(CO){PPh3–n(OC9H19)n}3] as the main species. The Rh‐catalysed hydroformylation of 1‐octene with these ligands was investigated in supercritical carbon dioxide (scCO2) and toluene as solvents. Although the catalytic systems are not soluble in scCO2, they are active. The activities are higher in toluene than in scCO2 but the selectivities for aldehydes in the case of the phosphonite derivative are higher in the supercritical medium than in toluene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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“…The product was purified by column chromatography (silica, eluent: CHCl-^/MeOH 95/5 v/v), giving 126 mg of 6 as a white crystalline solid: 1 H -N M R (90 MHz, CDC13) 8: 7.12 (d, 6 H, ArH, J 8 Hz), 6.90 (s, 3H, ArH CTV), 6 . 8 8 (d, 6 H, ArH, J 8 Hz), 6.60 (s, 3H, ArH CTV), 5.02 (s, 6 10. 7,8,d, Under an inert atmosphere, 0.3 ml (1.3 mmol) of diphenyl phosphochloridite was added to a solution of 126 mg (0.17 mmol) of 6 and 0.2 ml (1.3 mmol) of triethylamine in 10 mL of C H 2 C12.…”

mentioning

confidence: 99%