124-19-6Relevant articles and documents
Hydroformylation of internal olefins to linear aldehydes with novel rhodium catalysts
Van Der Veen, Lars A.,Kamer, Paul C.J.,Van Leeuwen, Piet W. N. M.
, p. 336 - 338 (1999)
Unprecedented high activities and selectivities were observed in the hydroformylation of internal octenes to linear products using rhodium catalysts with rigid diphosphane ligands. Dibenzophosphole 1 and a phenoxaphosphane analogue with bite angles of 120 and 119°, respectively, are suited for this.
Efficient hydroformylation in dense carbon dioxide using phosphorus ligands without perfluoroalkyl substituents
Koeken, Ard C. J.,Benes, Nieck E.,Van Den Broeke, Leo J. P.,Keurentjes, Jos T. F.
, p. 1442 - 1450 (2009)
Rhodium catalysts modified with triphenylphosphine, triphenyl phosphite, and tris(2,4-ditrrt-butylphenyl) phosphite have been evaluated for their performance in the hydroformylation of 1octene using carbon dioxide as the solvent. It is demonstrated that these catalysts are very efficient for the hydroformylation in carbon dioxide, although they are not designed for use in this medium. In particular, the catalyst prepared in situ from dicarbonyl(2,4-pentanedione)rhodium(I) and tris(2,4-di-tert-butyl-phenyl) phosphite gave rise to an initial turnover frequency in excess of 3x 10 4 molaldehyde molRh h-1. Such a reaction rate is unprecedented for hydroformylation in supercritical carbon dioxide-rich reaction mixtures.
Hsing,Chang
, p. 3589 (1939)
A facile method for promoting activities of ordered mesoporous silica-anchored Rh-P complex catalysts in 1-octene hydroformylation
Zhou, Wei,He, Dehua
, p. 1146 - 1154 (2009)
This work deals with the promotion of immobilized Rh catalyst activities in olefin hydroformylation by lengthening the alkyl spacers and choosing an active Rh precursor. The flexibility of long chain alkyls was used to free the motion of the anchored Rh c
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Goosen,Laue
, p. 383 (1969)
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Room-temperature production of bio-based aldehydes from vegetable oil-derived epoxide: via H2WO4?Al-MCM-41 as recyclable catalyst
Peng, Libo,Xie, Qinglong,Nie, Yong,Liu, Xuejun,Lu, Meizhen,Ji, Jianbing
, p. 23061 - 23070 (2019)
The oxidative cleavage of vegetable oils and their derivatives to produce bio-based aldehydes is a potentially useful process, although the aldehyde products are readily oxidized to carboxylic acids and thus seldom obtained in high yields. The present study developed a room-temperature method for the synthesis of bio-aldehydes via the oxidative cleavage of vegetable oil-derived epoxides, using H2WO4 as the catalyst, H2O2 as the oxidant, and t-BuOH as the solvent. Reactions were carried out at temperatures ranging from 25 to 35 °C for 3.5-10.5 h, and provided >99% conversion and >90% aldehyde yield. In particular, an approximately 97% yield was obtained at 25 °C after 10.5 h. As the reaction proceeded, the H2WO4 dissolved to form a W-containing anion. Several mesoporous Al-MCM-41 materials having different Si/Al ratios were hydrothermally synthesized and used as adsorbents to recover the catalyst by adsorbing these anions. The adsorption capacity of the Al-MCM-41 was found to increase with decreases in the Si/Al ratio. The Al-MCM-41 had little effect on the oxidative cleavage reaction at 25 °C, and thus could be directly added to the reaction system. The excellent anion adsorption performance of the Al-MCM-41 greatly improved the reusability of the H2WO4 catalyst. When using the Al-MCM-41 with the best adsorption performance, there was no significant decrease in the activity of the catalyst following five reuses.
Mediated electrolysis of vicinal diols by neocuproine palladium catalysts
Lybaert,Tehrani, K. Abbaspour,De Wael
, p. 685 - 691 (2017)
Synthetic electrochemistry agrees well with the principles of sustainable chemistry, therefore it is considered as a more environmentally friendly approach than some current synthetic methods. Here, we present a new strategy for the chemoselective oxidation of vicinal diols, viz. the integration of neocuproine palladium catalysts and electrosynthesis. Benzoquinones are used as an effective mediator as the reduced species (hydroquinones) can be easily reoxidized at relative low potentials at an electrode surface. NeocuproinePd(OAc)2 efficiently works as a catalyst in an electrolysis reaction for vicinal diols at room temperature. This is a remarkable observation given the fact that aerobic oxidation reactions of alcohols typically need a more complex catalyst, i.e. [neocuproinePdOAc]2[OTf]2. In this article we describe the optimization of the electrolysis conditions for the neocuproinePd(OAc)2 catalyst to selectively oxidize diols. The suggested approach leads to conversion of alcohols with high yields and provides an interesting alternative to perform oxidation reactions under mild conditions by the aid of electrochemistry.
Reactivity of platinum stanna-closo-dodecaborate complexes: First hydroformylation studies
Wesemann, Lars,Hagen, Siegbert,Marx, Thiemo,Pantenburg, Ingo,Nobis, Markus,Driessen-Hoelscher, Birgit
, p. 2261 - 2265 (2002)
The synthesis and characterization of two (dppp)Pt complexes with the stannaborate ligand SnB11H11 is described. In the case of the salt [Bu3MeN]2[(dppp)Pt (SnB11H11)2] the struc
Highly regioselective and active Rh-2,2′-bis(dipyrrolylphosphinooxy)- 1,1′-(±)-binaphthyl catalyst for hydroformylation of 2-octene
Liu, Wenjing,Yuan, Maolin,Fu, Haiyan,Chen, Hua,Li, Ruixiang,Li, Xianjun
, p. 596 - 597 (2009)
Rhodium catalyst bearing 2,2′-bis(dipyrrolyphosphinooxy)-1,1′- (±)-binaphthyl (ligand 1) shows high regioselectivity and activity for the hydroformylation of 2-octene. The introduction of a pyrrolyl group in the ligand greatly improves the yield of the linear aldehyde. The regioselectivity is up to 97.5% under mild conditions (100 °C, 0.7 MPa H2/CO). Copyright
Heterometallic catalysts. Cobalt carbonyl derivatives of lanthanides in catalysis of octene-1 hydroformylation
Beletskaya, I.P.,Magomedov, G.K.-I.,Voskoboinikov, A.Z.
, p. 289 - 295 (1990)
The results of an investigation involving the catalysis of octene-1 hydroformylation with heterobimetallic catalysts, cobalt carbonyl derivatives of lanthanides, are reported.
Realistic energy surfaces for real-world systems: An IMOMO CCSD(T):DFT scheme for rhodium-catalyzed hydroformylation with the 6-dppon ligand
Gellrich, Urs,Himmel, Daniel,Meuwly, Markus,Breit, Bernhard
, p. 16272 - 16281 (2013)
The hydroformylation of terminal alkenes is one of the most important homogeneously catalyzed processes in industry, and the atomistic understanding of this reaction has attracted enormous interest in the past. Herein, the whole catalytic cycle for rhodium-catalyzed hydroformylation with the 6-diphenylphosphinopyridine-(2H)-1-one (6-DPPon) ligand 1 was studied. This catalytic transformation is challenging to describe computationally, since two requirements must be met: 1) changes in the hydrogen-bond network must be modeled accurately and 2) bond-formation/bond-breaking processes in the coordination sphere of the rhodium center must be calculated accurately. Depending on the functionals used (BP86, B3LYP), the results were found to differ strongly. Therefore, the complete cycle was calculated by using highly accurate CCSD(T) computations for a PH3 model ligand. By applying an integrated molecular orbital plus molecular orbital (IMOMO) method consisting of CCSD(T) as high level and DFT as low-level method, excellent agreement between the two functionals was achieved. To further test the reliability of the calculations, the energetic-span model was used to compare experimentally derived and computed activation barriers. The accuracy of the new IMOMO method apparently makes it possible to predict the catalytic potential of real-world systems. Copyright
Amphiphilic Resin-Supported Rhodium-Phosphine Catalysts for C-C Bond Forming Reactions in Water
Uozumi, Yasuhiro,Nakazono, Maki
, p. 274 - 277 (2002)
Amphiphilic resin-supported rhodium-phosphine complexes were prepared on polystyrene-poly(ethylene glycol) graft co-polymer (1% DVB cross-linked) beads. The immobilized rhodium complexes exhibited high catalytic activity in water to promote hydroformylation of 1-alkenes, [2+2+2] cyclotrimerization of internal alkynes forming benzene rings, and 1,4-addition of arylboronic acids.
Selectivity of rhodium-catalyzed hydroformylation of 1-octene during batch and semi-batch reaction using trifluoromethyl-substituted ligands
Koeken, Ard C. J.,Van Vliet, Michiel C. A.,Van Den Broeke, Leo J. P.,Deelman, Berth-Jan,Keurentjes, Jos T. F.
, p. 179 - 188 (2008)
The regioselectivity of catalysts generated in situ from dicarbonyl rhodium(I)(2,4-pentanedione) and trifluoromethyl-substituted triphenylphosphine ligands has been evaluated during the hydroformylation of 1-octene. The influence of batch or semi-batch operation, the solvent, and the number of trifluoromethyl substituents has been investigated. During batch operation in a supercritical carbon dioxide (CO2)-rich system the differential n:iso ratio increases from approximately 4 to a value of 12-16 at about 90-95% conversion for the catalyst based on bis[3,5-bis(trifluoromethyl)phenyl] phenylphosphine. For semi-batch conditions using hexane a constant n:iso ratio is obtained over a broad conversion range. Batch hydroformylation in neat 1-octene is faster than in a supercritical CO2-rich, one-phase system, with a similar overall selectivity as observed in the supercritical case. The results provide further directions for the development of ligands that are especially designed for the separation of homogeneous catalysts in continuously operated hydroformylation in ScCO2.
Cobalt N-heterocyclic carbene alkyl and acyl compounds: Synthesis, molecular structure and reactivity
Llewellyn, Simon A.,Green, Malcolm L. H.,Cowley, Andrew R.
, p. 4164 - 4168 (2006)
The N-heterocyclic-carbene containing cobalt carbonyl compound [Co(IMes)(CO)3(Me)] (IMes = 1,3-bis(2,4,6-trimethylphenyl)-imidazol- 2-ylidene), 1, has been synthesised by tertiary phosphine displacement from [Co(PPh3)(CO)3(Me)]. Subsequent carbonylation afforded the acyl derivative [Co(IMes)(CO)3(COMe)], 2. Similarly, the compound [Co(IMes)(CO)3(COEt)], 3, has been synthesised. The compounds 2 and 3 have been shown to react with dihydrogen to form the cobalt hydride compound [Co(IMes)(CO)3(H)], 4. The molecular structures of compounds 1 and 2 have been determined. The Royal Society of Chemistry 2006.
Rhodium(I) Ferrocenylcarbene Complexes: Synthesis, Structural Determination, Electrochemistry, and Application as Hydroformylation Catalyst Precursors
Ramollo, G. Kabelo,López-Gómez, María J.,Liles, David C.,Matsinha, Leah C.,Smith, Gregory S.,Bezuidenhout, Daniela I.
, p. 5745 - 5753 (2015)
New examples of the rare class of rhodium(I) ferrocenyl Fischer carbene complexes 1-8, [Rh(LL)Cl{C(XR)Fc}] [LL = cod, (CO)2, (CO, PR3) (R = Ph, Cy or OPh), and (CO, AsPh3); XR = OEt or NHnPr] were prepared, and the electronic effects of coligands and alkoxy vs aminocarbene substituents were investigated by spectroscopic and electrochemical methods. The molecular structures of complexes 1, 2, and 4-6 were confirmed by single-crystal X-ray diffraction. The use of the complexes 1-8 as homogeneous catalysts for the hydroformylation of 1-octene was demonstrated, and the influence of the carbene substituents and coligands on the activity and regioselectivity of the catalysts evaluated. Finally, the stability of the Rh-Ccarbene bond of complex 1 under hydroformylation conditions was confirmed with 13C NMR experiments.
Linear amphiphilic TEMPO-grafted poly(ether sulfone) as polymeric interfacial catalyst: Synthesis, self-assembly behavior, and application
Chen, Liang,Tang, Jun,Zhang, Qi,Wang, Jianli
, p. 134 - 139 (2016)
In this study, we report the development of a novel recyclable polymer-supported interfacial catalyst for Montanari oxidation. The catalyst was prepared by immobilization of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) on poly(ether sulfone) (PES) bridged by imidazole groups and characterized by 1H nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, elemental analysis, contact angle measurement, and transmission electron microscopy (TEM). This well-designed polymer was self-assembled into nanoaggregates in CH2Cl2. It was then used as Pickering emulsifier in Montanari oxidation system (NaClO/NaBr/immobilized TEMPO) for selective oxidation of different alcohols, which exhibited higher activity due to the enhanced mass transfer through microreactor mechanism. Moreover, this polymeric interfacial catalyst was pH-sensitive and could be easily recycled by adding small amount of acid, and subsequent cycles of alcohol oxidation showed no loss on either conversion or selectivity. This study represents an innovative approach for developing polymeric interfacial catalyst.
Reaction Activity and Selectivity as a Function of Solution Ionic Strength in Oct-1-ene Hydroformylation with Sulfonated Phosphines
Ding, Hao,Hanson, Brian E.
, p. 2747 - 2748 (1994)
Salt concentration has a considerable influence on the activity and selectivity of water-soluble hydroformylation catalysts derived from Rh(acac)(CO)2 and the sulfonated phosphine, P3; addition of Na2SO4 or Na2HPO4 to the catalysts enhances the both the rate and selectivity of the hydroformylation reaction.
High pressure infrared and nuclear magnetic resonance studies of the rhodium-sulfoxantphos catalysed hydroformylation of 1-octene in ionic liquids
Silva, Silvana M.,Bronger, Raymond P. J.,Freixa, Zoraida,Dupont, Jairton,Van Leeuwen, Piet W. N. M.
, p. 1294 - 1296 (2003)
The rhodium-sulfoxantphos catalysed hydroformylation of 1-octene in 1-n-butyl-3-methylimidazoliuni hexafluorophosphate (BMI·PF6) as a room temperature ionic liquid was monitored in situ by high pressure IR (HP-IR) and NMR (HP-NMR). Similar ee (bis-equatorial) and ea (equatorial-apical) (diphosphine)Rh(CO)2H catalytic species, as observed in organic solvents, are formed in the BMI·PF6 ionic liquid. The ratio of the ee and ea isomers is influenced by both the temperature and syngas pressure. An increase in hydrogen partial pressure has no effect on the activity of the system during the reaction performed in BMI:PF6, while some hydroformylation systems using xanthene backbone ligands in conventional organic solvents can be sensitive to hydrogen partial pressure.
β-Cyclodextrin-Modified Diphosphanes as Ligands for Supramolecular Rhodium Catalysts
Reetz, Manfred T.,Waldvogel, Siegfried R.
, p. 865 - 867 (1997)
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Continuous, selective hydroformylation in supercritical carbon dioxide using an immobilised homogeneous catalyst
Meehan,Sandee,Reek,Kamer,Van Leeuwen,Poliakoff
, p. 1497 - 1498 (2000)
A continuous process for the selective hydroformylation of higher olefins in supercritical carbon dioxide (scCO2) is presented; the catalyst shows high selectivity and activity over several hours and no decrease in performance was observed over several days.
Silica gel supported ferric nitrate: A convenient oxidizing reagent
Khadilkar, Bhushan,Borkar, Shobha
, p. 207 - 212 (1998)
A silica gel supported ferric nitrate was prepared by co-grinding Fe(NO3)3.9H2O with silica gel in appropriate amounts. The reagent was used in equimolar quantity to oxidize various alcohols to corresponding aldehydes with complete selectivity. Similarly it successfully oxidizes various Hantzsch-type 1,4-dihydropyridines.
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Narasaka et al.
, p. 3724 (1972)
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Continuous flow homogeneous catalysis using supercritical fluids
Webb, Paul B.,Cole-Hamilton, David J.
, p. 612 - 613 (2004)
The continuous flow hydroformylation of 1-octene catalysed by Rh/[RMIM][Ph2PC6H4SO3] (R = 1-propyl, 1-pentyl or 1-octyl) dissolved only in the steady state reaction mixture and using scCO2 as a transport vector for both substrates and products gives rates up to 160-240 catalyst turnovers h-1 with low rhodium leaching over a 12 h period at a total pressure of 125-140 bar.
Mechanistic insights into a supramolecular self-assembling catalyst system: Evidence for hydrogen bonding during rhodium-catalyzed hydroformylation
Gellrich, Urs,Seiche, Wolfgang,Keller, Manfred,Breit, Bernhard
, p. 11033 - 11038 (2012)
The structural integrity and flexibility provided by intermolecular hydrogen bonds leads to the outstanding properties of the 6- diphenylphosphinopyridin-(2H)-1-one ligand (see scheme) in the rhodium-catalyzed hydroformylation of terminal alkenes, as demonstrated by the combination of spectroscopic methods and DFT computations. Hydrogen bonds were also detected in a competent intermediate of the catalytic cycle. Copyright
Preparation of Polymer Supported Phosphine Ligands by Metal Catalyzed Living Radical Copolymerization and Their Application to Hydroformylation Catalysis
Cardozo, Andres F.,Manoury, Eric,Julcour, Carine,Blanco, Jean-Francois,Delmas, Henri,Gayet, Florence,Poli, Rinaldo
, p. 1161 - 1169 (2013)
A series of well-defined polystyrene-supported tertiary phosphine ligands were prepared by copper-catalyzed atom transfer radical polymerization (ATRP), involving direct copolymerization of styrene and 4-diphenylphosphinostyrene (or 4-styryldiphenylphosphine, SDPP). Copolymerization of the two monomers at different molar ratios showed a decreasing level of control as the SDPP molar fraction (fSDPP) increased. A satisfactory level of control was achieved for fSDPP≤0.25 such that there was a constant concentration of growing living chains , and linear Mn growth with conversion and low dispersity. Copper-free polymers with different chain lengths were prepared and tested as polymeric ligands in the rhodium-catalyzed hydroformylation of 1-octene. The polymeric ligands yielded higher linear/branched selectivity and lower activity relative to PPh3 at the same P/Rh ratio. The selectivity increased slightly as a function of the polymer chain length.
Functionalized-1,3,4-oxadiazole ligands for the ruthenium-catalyzed Lemieux-Johnson type oxidation of olefins and alkynes in water
Hkiri, Shaima,Touil, Soufiane,Samarat, Ali,Sémeril, David
, (2021/11/30)
Three arene-ruthenium(II) complexes bearing alkyloxy(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-trifluoromethylphenyl)methyl ligands were quantitatively obtained through the reaction of (E)-1-(4-trifluoromethylphenyl)-N-(5-phenyl-1,3,4-oxadiazol-2-yl)-methanimine with the ruthenium precursor [RuCl2(η6-p-cymene)]2 in a mixture of the corresponding alcohol and CH2Cl2 at 50 °C. The obtained complexes were fully characterized by elemental analysis, infrared, NMR and mass spectrometry. Solid-state structures confirmed the coordination of the 1,3,4-oxadiazole moiety to the ruthenium center via their electronically enriched nitrogen atom at position 3 in the aromatic ring. These complexes were evaluated as precatalysts in the Lemieux-Johnson type oxidative cleavage of olefins and alkynes in water at room temperature with NaIO4 as oxidizing agent. Good to full conversions of olefins into the corresponding aldehydes were measured, but low catalytic activity was observed in the case of alkynes. In order to get more insight into the mechanism, three analogue arene-ruthenium complexes were synthesized and tested in the oxidative cleavage of styrene. The latter tests clearly demonstrated the importance of the hemilabile alkyloxy groups, which may form more stable (N,O)-chelate intermediates and increase the efficiency of the cis-dioxo-ruthenium(VI) catalyst.
Biobased Aldehydes from Fatty Epoxides through Thermal Cleavage of β-Hydroxy Hydroperoxides**
De Dios Miguel, Thomas,Duc Vu, Nam,Lemaire, Marc,Duguet, Nicolas
, p. 379 - 386 (2020/11/30)
The ring-opening of epoxidized methyl oleate by aqueous H2O2 has been studied using tungsten and molybdenum catalysts to form the corresponding fatty β-hydroxy hydroperoxides. It was found that tungstic acid and phosphotungstic acid gave the highest selectivities (92–93 %) towards the formation of the desired products, thus limiting the formation of the corresponding fatty 1,2-diols. The optimized conditions were applied to a range of fatty epoxides to give the corresponding fatty β-hydroxy hydroperoxides with 30–80 % isolated yields (8 examples). These species were fully characterized by 1H and 13C NMR spectroscopy and HPLC-HRMS, and their stability was studied by differential scanning calorimetry. The thermal cleavage of the β-hydroxy hydroperoxide derived from methyl oleate was studied both in batch and flow conditions. It was found that the thermal cleavage in flow conditions gave the highest selectivity towards the formation of aldehydes with limited amounts of byproducts. The aldehydes were both formed with 68 % GC yield, and nonanal and methyl 9-oxononanoate were isolated with 57 and 55 % yield, respectively. Advantageously, the overall process does not require large excess of H2O2 and only generates water as a byproduct.
Bio-derived nanosilica-anchored Cu(II)-organoselenium complex as an efficient retrievable catalyst for alcohol oxidation
Gogoi, Rajjyoti,Borah, Geetika
, (2021/09/13)
A new copper(II) complex supported onto rice-husk-derived nanosilica was prepared from 2,6-bis((phenylselanyl)methyl)pyridine, salicylaldehyde and copper acetate monohydrate, Cu(OAc)2·H2O. The as-synthesized complex Cu(II)SeNSe@imine-nanoSiO2 (Complex I) was extensively characterized with FT-IR, powder XRD, SEM-EDX, solid-state UV-Vis, ESR, XPS, TGA and BET surface area analysis. The catalytic activity of the complex was explored for alcohol oxidation reactions using H2O2 as oxidant and acetonitrile as solvent. For comparison, we have also prepared an analogous homogeneous catalyst (Complex II) and characterized it with FT-IR, UV-Vis, LC-MS and ESR analyses. Its catalytic activity was also screened to the same reaction. The immobilized catalyst showed better efficiency with 75%–95% isolated yield compared with the homogeneous one for alcohol oxidation with at least five times recyclability without profound loss in activity.