Xi:Irritant;
111-71-7Relevant academic research and scientific papers
Preparation and catalytic properties of resin bound binuclear rhodium tetracarboxylate complexes
Andersen, Jo-Ann M.,Karodia, Nazira,Miller, David J.,Stones, Duane,Gani, David
, p. 7815 - 7818 (1998)
4-(4'-Polystyryimethyloxy)-3-carboxylatomethyloxy-1-phenylacetate bis- μ-coordinated rhodium(II) diacetate complex, a resin-bound analogue of dirhodium tetraacetate in which two adjacent μ-bridging acetate moleties are covalently linked, serves as an efficient, stable and re-useable immobilised alkene hydrofomylation and hydrogenation catalyst.
Selectivity of catalytic systems RhCl3·polycation in hydroformylation of hex-1-ene under conditions of biphase catalysis
Kolesnichenko,Sharikova,Murzabekova,Markova,Slivinskii
, p. 1866 - 1869 (1996)
Approaches to increasing the selectivity of water-soluble catalytic systems based on RhCl3 and polycation in hydroformylation of hex-1-ene were studied. The introduction of a long-chain alkyl radical into the polycation or the use of a higher fatty acid anion results in an increase in the selectivity of the catalytic system at pH > 7 with respect to n-aldehyde to 60 %. This effect is presumably associated with the suppression of isomerization processes due to steric hindrances.
Low pressure catalytic hydroformylation of 1-hexene by the carbonylhydrido-tris(triphenylphosphine)rhodium(I), RhH(CO)(PPh3)3, in association with phosphinomethylzirconium complexes
Choukroun, R.,Gervais, D.,Kalck, P.,Senocq, F.
, p. C9 - C12 (1987)
Low pressure catalytic hydroformylation of 1-hexene was performed in the presence of RhH(CO)(PPh3)3 in association with diphenylphosphinomethylzirconium complexes such as Cp2Zr(CH2PPh2)2 and 2O or in the presence of bis(diphenylphosphine)butane.An isolated rhodium-zirconium complex, formulated as , was found to be catalytically active.
Investigations on the kinetics of hydroformylation of 1-hexene using HRh(CO)(PPh3)3 encapsulated hexagonal mesoporous silica as a heterogeneous catalyst
Sudheesh,Sharma, Sumeet K.,Shukla, Ram S.,Jasra, Raksh V.
, p. 23 - 29 (2010)
Kinetics of HRh(CO)(PPh3)3 encapsulated in hexagonal mesoporous silica has been investigated for the heterogeneous catalyzed hydroformylation of 1-hexene. The rates of hydroformylation of C5-C12 alkenes, determined under identical conditions, indicated a decreasing trend on increasing the chain length of the alkenes. The representative alkene, 1-hexene has been subjected for detail kinetic investigations. The 1-hexene hydroformylation kinetics has been studied as the function of the amount of catalyst, concentration of 1-hexene, partial pressure of CO and H2, and temperature. All these parameters were found to influence the rate of hydroformylation. The rate was observed to be first order with respect to partial pressure of hydrogen. The rate was observed to increase with the increase in the amount of the catalyst and approached saturation on increasing the catalyst amount. Rates increased on increasing the CO pressure and 1-hexene concentration up to certain values, and on further increasing these parameters, substrate inhibited kinetics was observed for both CO and 1-hexene at higher pressures and concentrations, respectively. A kinetic rate model based on the mechanism of hydroformylation of 1-hexene was found to fit with the experimental rate with ±15% deviation.
Sulphur-containing Dinuclear Rhodium Complexes as Catalyst Precursors for the Selective Hydroformylation of Alkenes
Kalck, Philippe,Frances, Jean-Marc,Pfister, Pierre-Marie,Southern, Timothy G.,Thorez, Alain
, p. 510 - 511 (1983)
Dinuclear thiolato bridged complexes, particularly 2>, catalyse the hydroformylation of hex-1-ene at low pressure and temperature to afford selectively and with high turnover rates the corresponding aldehydes.
Hydroformylation of 1-Hexene in Supercritical Carbon Dioxide: Characterization, Activity, and Regioselectivity Studies
Marteel, Anne E.,Tack, Timothy T.,Bektesevic, Selma,Davies, Julian A.,Mason, Mark R.,Abraham, Martin A.
, p. 5424 - 5431 (2003)
The hydroformylation of alkenes is a major commercial process used for the production of oxygenated organic compounds. When the hydroformylation reaction is performed using a homogeneous catalyst, an organic or aqueous solvent is employed, and a significant effort must be expended to recover the catalyst so it can be recycled. Development of a selective heterogeneous catalyst would allow simplification of the process design in an integrated system that minimizes waste generation. Recent studies have shown that supercritical carbon dioxide (scCO2) as a reaction solvent offers optimal environmental performance and presents advantages for ease of product separation. In particular, we have considered the conversion of 1-hexene to heptanal using rhodium- and platinum-phosphine catalysts tethered to supports insoluble in scCO2 to demonstrate the advantages and to understand the limitations of a solid-catalyzed process. One of the historical limitations of supported catalysts is the inability to control product regioselectivity. To address this concern, we have developed tethered catalysts with phosphinated silica and controlled pore size MCM-41 and MCM-20 supports that provide improved regioselectivity and conversion relative to their nonporous equivalents. Platinum catalysts supported on MCM-type supports were the most regioselective whereas the analogous rhodium catalysts were the most active for hydroformylation of 1-hexene in scCO2.
Study of reaction and kinetics in pyrolysis of methyl ricinoleate
Guobin, Han,Zuyu, Liu,Suling, Yao,Rufeng, Yan
, p. 1109 - 1112 (1996)
The effects of pyrolysis temperature, space-velocity, and dilution ratio of starting materials on the reaction have been studied in the pyrolysis of methyl ricinoleate. The reaction parameters were optimized to obtain yield ranges of 25.8-26.7% for heptaldehyde and 45.7-46.5% for methyl undecenoate. The kinetic study showed that pyrolysis of methyl ricinoleate is a first-order reaction at 828-878 K, and the activation energy is 1.729 × 105 J/mol.
Highly regioselective hydroformylation of higher olefins catalysed by rhodium-phosphine complexes in ionic liquid medium
Lin, Qi,Fu, Haiyan,Jiang, Weidong,Chen, Hua,Li, Xianjun
, p. 216 - 220 (2007)
Hydroformylation of higher olefins was performed efficiently in ionic liquids 1-n-alkyl-3-methylimidazolium p-toluenesulfonate ([Rmim][p-CH 3C6H4SO3], R = n-butyl, n-octyl, n-dodecyl, n-cetyl) with the rhodium-phosphine complex Rh-BISBIS (Rh = rhodium complex catalyst precursor; BISBIS = sodium salt of sulfonated 2,2′-bis (diphenylphosphinomethyl)-1,1′-biphenyl) as catalyst. The catalytic system offers excellent regioselectivity towards the linear aldehyde with high activity and chemoselectivity for aldehyde. Furthermore, the ionic liquid containing catalyst can be facilely separated and reused three times without a significant decrease in the activity and selectivity. The ionic liquids [Rmim][p-CH3C6H4SO3] used as the reaction media bring some definitive advantages over the halogen-containing analogues [bmim]BF4 and [bmim]PF6.
Hydroformylation in perfluorinated solvents; improved selectivity, catalyst retention and product separation
Foster, Douglas F,Gudmunsen, David,Adams, Dave J,Stuart, Alison M,Hope, Eric G,Cole-Hamilton, David J,Schwarz, Gary P,Pogorzelec, Peter
, p. 3901 - 3910 (2002)
The hydroformylation of linear terminal alkenes using rhodium based catalysts under fluorous biphasic conditions in the presence and absence of toluene is reported. Using fluorinated ponytails to modify triarylphosphites and triarylphosphines, good selectivities and reactivities can be obtained, along with good retention of the catalyst and ligand within the fluorous phase. Using P(O-4-C6H4C6F13)3 (P/Rh=3:1) as the ligand in toluene/perfluoro-1,3-dimethylcyclohexane, good results are obtained at 60°C, but decomposition of the catalyst and/or ligand occurs on increasing the temperature. More impressive results are obtained by omitting the toluene, with higher rates, better l/b ratios, and better retention of the catalyst and the phosphite within the perfluorocarbon solvent. Competing isomerisation restricts linear aldehyde selectivities to 6H4C6F13)3 is used as the ligand in the absence of toluene, even more impressive results can be obtained, with linear aldehyde selectivities up to 80.9%, high rates, and the retention of up to 99.95% of the rhodium and up to 96.7% of the phosphine within the fluorous phase. These results are compared with those of commercial systems for propene hydroformylation and with those previously reported in the literature for hydroformylation under fluorous biphasic conditions. Phase behaviour studies show that 1-octene is completely miscible with the fluorous solvent under the conditions used for the hydroformylation experiments, but that the product nonanal, phase separates.
Synthesis and Catalytic Evaluation of Phosphanylferrocene Ligands with Cationic Guanidinium Pendants and Varied Phosphane Substituents
Bárta, Ond?ej,Císa?ová, Ivana,Mieczyńska, Ewa,Trzeciak, Anna M.,?těpni?ka, Petr
, p. 4846 - 4854 (2019)
This contribution expands the still narrow class of functional ferrocene phosphanes with polar cationic groups, focusing on the synthesis and catalytic use of a series of phosphanylferrocene ligands bearing positively charged guanidinium tags, [R2PfcCH2NHC(NH2)2]Cl (3a–d), where fc = ferrocene-1,1′-diyl, R = isopropyl (a), cyclohexyl (b), phenyl (c), and 2-furyl (d). To probe the influence of phosphane substituents, these compounds were studied as supporting ligands in Pd-catalyzed Suzuki–Miyaura cross-coupling of acyl chlorides with arylboronic acids, in analogous coupling of aryl bromides with arylboronic acids, and in Rh-catalyzed hydroformylation of 1-hexene using trans-[RhCl(CO){R2PfcCH2NHC(NH2)2-κP}2]Cl2 complexes (4a–d) as pre-catalysts. The outcome of the cross-coupling reactions strongly depended on the starting materials, and no ligand generated a universally applicable catalyst when combined with Pd(OAc)2. In the hydroformylation reactions, the catalyst based on 4d led to lower conversions than all others, which performed rather similarly. Overall, the phenyl-substituted phosphane 3c emerged as a good compromise, giving rise to reasonably efficient and stable catalysts in most cases (except for Suzuki–Miyaura biaryl cross-couplings, wherein electron-rich alkylphosphanes performed better than 3c).
