- A new biogenerated Rh-based catalyst for aqueous biphasic hydroformylation
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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.
- Paganelli, Stefano,Piccolo, Oreste,Baldi, Franco,Gallo, Michele,Tassini, Riccardo,Rancan, Marzio,Armelao, Lidia
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- Chemo- And regioselective hydroformylation of alkenes with CO2/H2over a bifunctional catalyst
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As is well known, CO2 is an attractive renewable C1 resource and H2 is a cheap and clean reductant. Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging topic in green chemistry. A general and selective rhodium-catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here. With this protocol, the desired aldehydes can be obtained in up to 97% yield with 93/7 regioselectivity under mild reaction conditions (25 bar and 80 °C). The key to success is the use of a bifunctional Rh/PTA catalyst (PTA: 1,3,5-triaza-7-phosphaadamantane), which facilitates both CO2 hydrogenation and hydroformylation. Notably, monodentate PTA exhibited better activity and regioselectivity than common bidentate ligands, which might be ascribed to its built-in basic site and tris-chelated mode. Mechanistic studies indicate that the transformation proceeds through cascade steps, involving free HCOOH production through CO2 hydrogenation, fast release of CO, and rhodium-catalyzed conventional hydroformylation. Moreover, the unconventional hydroformylation pathway, in which HCOOAc acts as a direct C1 source, has also been proved to be feasible with superior regioselectivity to that of the CO pathway.
- Hua, Kaimin,Liu, Xiaofang,Wei, Baiyin,Shao, Zilong,Deng, Yuchao,Zhong, Liangshu,Wang, Hui,Sun, Yuhan
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supporting information
p. 8040 - 8046
(2021/11/01)
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- Rh-catalyzed highly regioselective hydroformylation to linear aldehydes by employing porous organic polymer as a ligand
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In this work, we developed a new structural porous organic polymer containing biphosphoramidite unit, which can be used as a solid bidentate phosphorous ligand for rhodium-catalyzed solvent-free higher olefins hydroformylation. The resultant catalyst demonstrated unprecedently high regioselectivity to linear aldehydes and could be readily recovered for successive reuses with good stability in both catalytic activity and regioselectivity. This journal is
- Wang, Zhaozhan,Yang, Yong
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p. 29263 - 29267
(2020/10/06)
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- A modular family of phosphine-phosphoramidite ligands and their hydroformylation catalysts: steric tuning impacts upon the coordination geometry of trigonal bipyramidal complexes of type [Rh(H)(CO)2(P^P?)]
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Four new phosphine-phosphoramidite bidentate ligands have been synthesised and studied in rhodium-catalysed hydroformylation. Variable temperature NMR studies have been used along with HPIR to investigate the coordination mode of the trigonal bipyramidal complexes formed from [Rh(acac)(CO)2], ligand and syngas. It was found that small changes to the ligand structure have a large effect on the geometry of the active catalytic species. The rhodium catalysts of these new ligands were found to give unusually high iso-selectivity in the hydroformylation of propene and 1-octene.
- How, Rebecca C.,Hembre, Robert,Ponasik, James A.,Tolleson, Ginette S.,Clarke, Matthew L.
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p. 118 - 124
(2015/12/31)
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- New tetraphosphite ligands for regioselective linear hydroformylation of terminal and internal olefins
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We successfully developed new tetraphosphite ligands L1-L5 and applied them to the rhodium-catalyzed hydroformylation of terminal and internal olefins. High catalytic reactivities and excellent regioselectivities for linear aldehydes were obtained in the rhodium-catalyzed hydroformylation of simple olefins (l/b ratio up to 90, 98.9% linear selectivity, 99.2% conversion) using the tetraphosphite ligand L2. And the tetraphosphite ligand L2 also displayed moderate to good linear regioselectivities for challenging substrates styrene and internal olefin 2-octene.
- Zhang, Zongpeng,Chen, Caiyou,Wang, Qian,Han, Zhengyu,Dong, Xiu-Qin,Zhang, Xumu
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p. 14559 - 14562
(2016/02/19)
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- Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid
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The invention relates to a method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on the basis of a phosphine-functionalized polyether imidazolium salt ionic liquid. According to the method, a two-phase catalytic system is adopted, the catalytic system comprises a phosphine-functionalized polyether imidazolium salt ionic liquid, a polyether imidazolium salt ionic liquid, a rhodium catalyst, a reaction substrate olefin and a reaction product aldehyde, a liquid/liquid two-phase hydroformylation reaction is performed at certain reaction temperature and under certain synthesis gas pressure, the rhodium catalyst is separated and cycled through simple two-phase separation after the reaction ends, the rhodium catalyst can be recycled multiple times, and the catalytic activity and the selectivity are not remarkably reduced. The TOF value of the system reaches 400-3,300 h and the catalytic cycle accumulated TON value reaches 33,975.
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Paragraph 0051; 0079; 0080; 0081
(2017/11/17)
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- Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation-acetalization of olefins
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A series of ionic phosphonium-based aminophosphines L1-L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom. The molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well retained without incompatibility problems. Investigations on co-catalysis over L1-L3 showed that L3 exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine fragment in L3 was responsible for hydroformylation together with the Rh-complex and the phosphonium acted as the Lewis acidic catalyst in charge of acetalization. The L3-Rh(acac)(CO)2 system also exhibited good generality to hydroformylation-acetalization of a wide range of olefins in different alcohols.
- Wang, Peng,Liu, Huan,Li, Yong-Qi,Zhao, Xiao-Li,Lu, Yong,Liu, Ye
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p. 3854 - 3861
(2016/06/14)
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- From alkenes to alcohols by cobalt-catalyzed hydroformylation-reduction
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The cobalt-catalyzed hydroformylation of alkenes in the presence of a range of novel cyclic phosphine ligands was investigated. The effect of various parameters such as solvents, additives, cobalt/phosphine ratio, CO/H2 (1:2), and nature of the alkenes was examined. The results revealed that both terminal and internal alkenes are hydroformylated in high yields to give mainly linear products at moderate temperature and syn gas pressure. The linearity ranges from 43 to 85%, with Lim-10 giving the highest proportion of linear product.
- Achonduh, George,Yang, Qian,Alper, Howard
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supporting information
p. 1241 - 1246
(2015/03/05)
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- Method for Producing Isononanoic Acid Esters, Starting from 2-Ethyl Hexanol
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A Process for preparing carboxylic esters of a mixture of structurally branched C9 monocarboxylic acids proceeding from 2-ethylhexanol is characterized in that (a) 2-ethylhexanol is dehydrated to an octene mixture in the presence of a catalyst; (b) the octene mixture obtained in step a) is reacted in the presence of a transition metal compound of group VIII of the periodic table of the elements with carbon monoxide and hydrogen to give a mixture of isomeric isononanals; (c) the mixture of isomeric isononanals obtained in step b) is oxidized to a mixture of structurally branched C9 monocarboxylic acids; and (d) the mixture of structurally branched C9 monocarboxylic acids obtained in step c) is reacted with alcohols to give carboxylic esters.
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Paragraph 0077-0080; 0083
(2015/06/17)
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- Method for Producing Isononanoic Acids from 2-Ethyl Hexanol
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Process for preparing isononanoic acid proceeding from 2-ethylhexanol, characterized in that (a) 2-ethylhexanol is dehydrated to octene in the presence of a catalyst; (b) the octene obtained in step a) is reacted in the presence of a transition metal compound of group VIII of the periodic table of the elements with carbon monoxide and hydrogen to give isononanal; and (c) the isononanal obtained in step b) is oxidized to isononanoic acid.
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Paragraph 0062-0068
(2015/07/15)
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- Molybdenum carbonyl grafted onto silicate intercalated cobalt-aluminum hydrotalcite: A new potential catalyst for the hydroformylation of octene
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We present the first example of molybdenum carbonyl grafted on diaminosiloxane-functionalized cobalt-aluminum hydrotalcite (CA-HTSi-DA-Mo) as a promising catalyst for the hydroformylation of olefins. The catalyst showed 80% conversion with selective formation of branched aldehyde. About 70% of the catalytic activity retains even after three cycles.
- Sakthivel, Ayyamperumal,Mahato, Nihar Ranjan,Baskaran, Thangaraj,Christopher, Jayaraj
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- METHOD FOR HYDROFORMYLATION OF UNSATURATED COMPOUNDS
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The invention relates to a method for hydroformylation of unsaturated compounds such as olefins and alkynes using mixtures of synthesis gas (CO/H2), in which either the unsaturated compounds and a catalyst are heated to a reaction temperature of 60 to 200° C. and the synthesis gas is then added, or the unsaturated compounds and the catalyst are brought into contact with pure CO at normal temperature in a preformation step, then are heated to reaction temperature and on reaching the reaction temperature the CO is replaced by the synthesis gas. The pressure is 1 to 200 bar and the CO:H2 ratio in the synthesis gas is in the range from 1:1 to 50:1. The iridium catalyst used comprises a phosphorus-containing ligand in the iridium:ligand ratio in the range from 1:1 to 1:100. With high catalyst activities and low catalyst use, very high turnover frequencies are achieved.
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Paragraph 0073
(2014/02/16)
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- Bulky phosphinines: From a molecular design to an application in homogeneous catalysis
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The design and preparation of an asymmetrically substituted and bulky phosphinine was achieved by introducing sterically demanding substituents into specific positions of a rigid phosphorus-heterocyclic framework. Compound 5 shows, at the same time, axial chirality and a sufficiently high energy barrier for internal rotation to prevent enantiomerization. Both enantiomers of 5 were isolated by means of chiral analytical HPLC, and their absolute configurations could be assigned by combining experimental data and DFT calculations. Despite its substitution pattern, 5 can still coordinate to transition-metal centers through the lone pair of electrons on the phosphorus atom. Rapid C-H activation on the adjacent aryl substituent at the 2-position of the phosphorus heterocycle was achieved by using [{CpIrCl2}2] (Cp=1,2,3,4,5- pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of 5 was applied as a π-accepting low-coordinate phosphorus ligand in the Rh-catalyzed hydroformylation of trans-2-octene, which showed a clear preference for the formation of 2-methyloctanal. Bulky phosphinines: An asymmetrically substituted, bulky, and atropisomeric phosphinine has been prepared and characterized (see figure). Rapid C-H activation on the 2-aryl substituent of the phosphorus heterocycle was achieved with [{CpIrCl2}2] (Cp=1,2,3,4,5-pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of the phosphinine acted as a π-accepting low-coordinate phosphorus ligand in the Rh-catalyzed hydroformylation of 2-octene. Copyright
- Weemers, Jarno J. M.,Van Der Graaff, Willem N. P.,Pidko, Evgeny A.,Lutz, Martin,Mueller, Christian
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p. 8991 - 9004
(2013/07/25)
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- Ligand-metal cooperating PC(sp3)P pincer complexes as catalysts in olefin hydroformylation
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Ligand-metal cooperation: A new ligand-metal cooperating catalyst for the hydroformylation of olefins is described (see scheme). The mechanism of the H2 activation and C-H bond formation of the catalyst involves an intramolecular cooperation between the structurally remote functionality and the metal center and proceeds without change of the oxidation state of the metal.
- Musa, Sanaa,Filippov, Oleg A.,Belkova, Natalia V.,Shubina, Elena S.,Silantyev, Gleb A.,Ackermann, Lutz,Gelman, Dmitri
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supporting information
p. 16906 - 16909
(2014/01/06)
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- CATALYST AND METHOD HAVING SELECTIVITY TO ISOBUTYRALDEHYDE VIA CATALYST INDUCTION
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Industrially relevant product selectivities and reaction rates are obtained from rhodium catalyzed hydroformylation of propylene via the use of a novel induction period in which the supramolecular ligand assembly, the rhodium precatalyst and an initial substrate are allowed to form a hydroformylation catalyst that is more selective toward branched aldehydes. Upon heating this incubated mixture and addition of propylene, iso-butyraldehyde is obtained in higher concentrations and rates that are otherwise unattainable.
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Paragraph 0055; 0056
(2014/01/07)
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- CATALYSTS AND PROCESSES FOR PREPARING ALDEHYDES
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Use of a unique supramolecular assembly of a pyridylphosphine ligand and a metal centered porphyrin complex is shown to give unprecedented selectivities to branched aldehydes via rhodium catalyzed hydroformylation of unsubstituted linear alpha-olefins such as propylene and 1-octene. Increasing the syngas pressure is shown to have a beneficial effect on branched aldehyde selectivity as is increasing the ratio of carbon monoxide to hydrogen used in the hydroformylation reaction.
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Paragraph 0033
(2014/01/07)
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- Highly active hydroformylation catalysts: Synthesis, characterisation and catalytic performance
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The phoszone ligand [(Ph2P)(bis-3,5-CF3-Ph)]NN= CH(penta-fluoro-Ph) transformed in liquid CO2 at room temperature in presence of [Rh(cod)2]OTf into [Rh(cod)(η2-P,P′- Ph2POPPh2)]OTf. Replacing the O-atom in Ph 2POPPh2 by a PrN-group leads to the ligand PrN(PPh 2)2 acting similarly as a bidentate ligand in [Rh(cod)(η2-P,P′-PrN(PPh2)2)]OTf. Hydroformylation of 1-octene with in situ catalysts formed by the ligands with [Rh(cod)2]OTf showed hydroformylation activities at 50 % conversion of 16,000 h-1 (PrN(PPh2)2/[Rh(cod) 2]OTf) and 24,000 h-1 (phoszone/[Rh(cod)2]OTf), respectively.
- Piras, Elisabetta,Powietzka, Bernhard,Wurst, Frederik,Neumann-Walter, Doreen,Gruetzmacher, Hans-Joerg,Otto, Thomas,Zevaco, Thomas,Walter, Olaf
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p. 673 - 680
(2013/07/26)
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- A bulky phosphite modified rhodium catalyst for efficient hydroformylation of disubstituted alkenes and macromonomers in supercritical carbon dioxide
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The hydroformylation of disubstituted alkenes and related macromonomers in supercritical CO2 is demonstrated. Higher turnover frequencies were observed for the 1,2-disubstituted alkenes than for the 1,1-disubstituted alkenes. The turnover frequency for poly(styrene) macromonomer hydroformylation compares well with that observed for cyclohexene. The turnover frequency observed for poly(methyl methacrylate) macromonomer hydroformylation is considerably lower than that observed for methyl methacrylate. Unprecedented turnover frequencies are observed in comparison with previous studies where CO2 has been applied as a solvent. This is achieved using rhodium modified with a readily available bulky phosphite ligand without the need of ligand modification to improve solubility in supercritical CO2.
- Koeken, Ard C. J.,Smeets, Niels M. B.
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p. 1036 - 1045
(2013/04/24)
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- From olefins to alcohols: Efficient and regioselective ruthenium-catalyzed domino hydroformylation/reduction sequence
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Exploring the alternatives: Ruthenium imidazoyl phosphine complexes catalyze the domino hydroformylation/reduction of alkenes to alcohols in good yields and with good selectivities (see scheme). Linear aliphatic alcohols are synthesized under reaction conditions typically used in industrial hydroformylations. Copyright
- Fleischer, Ivana,Dyballa, Katrin Marie,Jennerjahn, Reiko,Jackstell, Ralf,Franke, Robert,Spannenberg, Anke,Beller, Matthias
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supporting information
p. 2949 - 2953
(2013/04/10)
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- Bis-(thiosemicarbazonato) Zn(II) complexes as building blocks for construction of supramolecular catalysts
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In this paper we report the application of bis-(thiosemicarbazonato) Zn(II) complexes as building blocks in the construction of supramolecular transition metal assemblies. We investigated their coordination behaviour towards pyridylphosphine molecules and found these systems comparable to those based on Zn(porphyrin) and Zn(salphen) complexes. Additionally, catalytic experiments and an in situ high-pressure FTIR study of the supramolecular rhodium hydroformylation catalysts, assembled using the bis-(thiosemicarbazonato) Zn(II) complexes, demonstrate their applicability in supramolecular catalysis and their potential for application in other areas of supramolecular chemistry. The Royal Society of Chemistry 2012.
- Bocokic, Vladica,Lutz, Martin,Spek, Anthony L.,Reek, Joost N. H.
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experimental part
p. 3740 - 3750
(2012/05/07)
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- Coordination studies on supramolecular chiral ligands and application in asymmetric hydroformylation
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In this study we introduce a series of monodentate pyridine-based ligands for which the phosphorus coordination mode to rhodium can be controlled by the binding of ZnII-templates to the pyridyl group. A series of monodentate phosphoroamidite and phosphite ligands have been prepared and studied under hydroformylation conditions by in situ high-pressure NMR and IR techniques. These studies reveal the exclusive formation of rhodium hydride complexes in which the phosphorus atom of the ligand resides in an axial position, trans to the hydride, but only after addition of Zn II-template. In the absence of these templates the usual mono-coordinated rhodium hydrido complexes are formed, with the phosphorus ligated in the equatorial plane, cis to the hydride. The catalytic performance of these complexes is evaluated in asymmetric hydroformylation of unfunctionalised internal alkenes in which the supramolecular change is reflected in higher activity and selectivity.
- Bellini, Rosalba,Reek, Joost N. H.
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supporting information; experimental part
p. 7091 - 7099
(2012/07/27)
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- Highly regioselective isomerization-hydroformylation of internal olefins catalyzed by rhodium/tetraphosphine complexes
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A new class of substituted tetraphosphine ligands has been applied in the rhodium-catalyzed regioselective isomerization-hydroformylation of internal olefins. The rhodium/tetraphosphine ligand system is highly effective for the isomerization and hydroformylation of 2-alkenes to form linear aldehydes. Greater than 95% linear selectivity and up to 94% yield of the total aldehydes were obtained for 2-pentene, 2-hexene and 2-octene. The catalyst system also showed high to moderate linear selectivity for the isomerization and hydroformylation of 3-hexene, 3-octene and 4-octene but with slow reaction rates. Copyright
- Cai, Chaoxian,Yu, Shichao,Liu, Guodu,Zhang, Xumu,Zhang, Xiaowei
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scheme or table
p. 2665 - 2670
(2011/12/16)
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- Supramolecular control of ligand coordination and implications in hydroformylation reactions
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The coordination mode of a monodentate phosphoroamidite ligand in a rhodium complex can be switched from equatorial to axial by a unique supramolecular pseudo encapsulation (see scheme). The axial complex has higher activity and selectivity in the challenging asymmetric hydroformylation of internal alkenes. Copyright
- Bellini, Rosalba,Chikkali, Samir H.,Berthon-Gelloz, Guillaume,Reek, Joost N. H.
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supporting information; experimental part
p. 7342 - 7345
(2011/10/04)
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- Full kinetic description of 1-octene hydroformylation in a supercritical medium
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The kinetics of the hydroformylation of 1-octene in a supercritical carbon dioxide medium, catalyzed by a tris(3,5-bis[trifluoromethyl]phenyl)phosphine- modified rhodium catalyst, have been investigated. The influence of the concentration of carbon dioxid
- Koeken, Ard C.J.,Van Den Broeke, Leo J.P.,Deelman, Berth-Jan,Keurentjes, Jos T.F.
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scheme or table
p. 1 - 11
(2011/10/12)
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- Aqueous-biphasic hydroformylation of alkenes promoted by "weak" surfactants
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The aqueous-biphasic hydroformylation of higher alkenes catalyzed by Rh/TPPTS has been carried out in the presence of imidazolium, pyridinium and triethylammonium salts. High reaction rates are achieved with imidazolium and triethylammonium salts provided that their alkyl "tail" is ≥C 8. Fast and complete phase separation, and good retention of the metal in the aqueous phase could be achieved with an octyl "tail". Imidazolium salts were found to give the highest rate enhancement. The nature of the anion showed a moderate influence on the reaction. Evidence suggests that the additive can act as weak surfactant allowing emulsions to be formed and broken by simply switching the stirring on and off.
- Desset, Simon L.,Reader, Simon W.,Cole-Hamilton, David J.
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experimental part
p. 630 - 637
(2010/04/29)
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- Indenyl- and fluorenyl-functionalized n-heterocyclic carbene complexes ofrhodium and iridium synthetic, structural and catalytic studies
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Rhodium and iridium complexes with N-heterocyclic carb-enes (NHC) functionalized with neutral or anionic indenyland fluorenyl groups are reported. In the complexes the li-gands adopt monodentate, bidentate or bridging bondingmodes with the NHC group ?-bonded and the fluorenyl orindenyl functionalities either dangling or coordinated to themetal with various hapticities (?1, ?3 and ?5). Metallation ofthe C-H bond of the alkylene linker in the ligand has also been observed. Catalytic studies on the bidentate RhIcom-plex 6 show that it is weakly active for the hydroformylationof 1-octene with poor linear selectivity, but it shows slightlylower activity than the standardMonsanto system for the car-bonylation of methanol. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.
- Downing, Stephen P.,Pogorzelec, Peter J.,Danopoulos, Andreas A.,Cole-Hamilton, David J.
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experimental part
p. 1816 - 1824
(2009/10/30)
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- CATALYST PRECURSOR FOR AN Rh COMPLEX CATALYST
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The present invention relates to the preparation and use of stable catalyst precursors of rhodium complex catalysts.
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Page/Page column 9
(2009/12/05)
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- Metal-doped epoxy resins: Easily accessible, durable, and highly versatile catalysts
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Thermosetting epoxy resins, such as the triglycidyl derivative of 4-aminophenol, can be polymerized using molybdenum, palladium, or rhodium complexes as initiators. The resulting metal-doped materials proved to be efficient catalysts for epoxidation, carbon-carbon coupling, hydrogenation, and hydroformylation reactions. Propylene oxide yields of around 50% were obtained in the epoxidation of propylene with tert-butyl hydroperoxide as the oxidant, and biphenyl yields of ≥98% were observed in the Suzuki coupling of iodobenzene with phenylboronic acid. Almost quantitative conversions were accomplished in the hydrogenation of ethyl crotonate, ethyl cinnamate, and croton aldehyde, whereas aldehyde yields of around 16% were obtained in the hydroformylation of 1-octene. Organic-inorganic hybrid catalysts can be obtained in a convenient one-step procedure by the addition of inorganic components to the liquid resins and subsequent polymerization. Different metal species can be combined in one thermoset matrix, affording multifunctional catalysts that can be us in various catalytic liquid-phase transformations. Quantification of metal traces in the reaction mixtures by metal enrichment and atomic spectroscopy demonstrated very low metal losses of the catalysts. The catalysts can be simply recovered by filtration and reused without reconditioning while maintaining stability, activity, and selectivity.
- Artner, Johannes,Bautz, Harald,Fan, Fengwen,Habicht, Wilhelm,Walter, Olaf,Doering, Manfred,Arnold, Ulrich
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p. 180 - 189
(2008/12/20)
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- Selectivity of rhodium-catalyzed hydroformylation of 1-octene during batch and semi-batch reaction using trifluoromethyl-substituted ligands
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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.
- Koeken, Ard C. J.,Van Vliet, Michiel C. A.,Van Den Broeke, Leo J. P.,Deelman, Berth-Jan,Keurentjes, Jos T. F.
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scheme or table
p. 179 - 188
(2009/04/08)
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- N-Acetyl-N,N-dipyrid-2-yl (cyclooctadiene) rhodium (I) and iridium (I) complexes: Synthesis, X-ray structures, their use in hydroformylation and carbonyl hydrosilylation reactions and in the polymerization of diazocompounds
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The synthesis of novel N-acetyl-N,N-dipyrid-2-yl complexes of RhI and IrI, i.e. [RhCl(CH3CONPy2)(COD)] (1) and [IrCl(CH3CONPy2)(COD)] (2), respectively, is described. Upon prolonged treatment in CH2Cl2 at room temperature, complex 1 is transformed into a cationic Rh-complex, i.e. [Rh(CH3CONPy2)(COD)+RhCl2(COD)-] (1a). Compound 1a crystallizes in the monoclinic space group P21/c, complex 2 crystallizes in the triclinic space group P over(1, ?). Compound 1 was investigated for its catalytic activity in the hydroformylation of cyclooctene as well as of 1-octene. In addition, 1 was used in various carbonyl hydrosilylation reactions of both aldehydes and ketones. There, turn-over numbers up to 50 000 and yields in the range of 85-100% were observed. Finally, compound 1 was successfully used for the polymerization of N2CHCOOEt yielding highly stereoregular poly(ethoxycarbonylcarbene) with Mw = 67 000 g/mol and a polydispersity index (PDI) of 2.59.
- Bantu, Bhasker,Wurst, Klaus,Buchmeiser, Michael R.
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p. 5272 - 5278
(2008/02/13)
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- Rhodium-catalyzed hydroformylation of olefins: Effect of [bis(2,4-di-tert-butyl) pentaerythritol] diphosphite (alkanox P-24) on the regioselectivity of the reaction
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Rhodium (I) associated with [bis(2,4-di-tert-butyl) pentaerythritol] diphosphite (I) as a ligand represents an active catalyst system for highly regioselective hydroformylation of various alkenes. The commercially available bis(2,4-di-tert-butyl)pentaerythritol diphosphite (alkanox P-24) (I), which has been used so far as an antioxidant in the stabilization of polymers, was used as a diphosphite ligand for the selective hydroformylation reaction of olefins. Excellent selectivity towards linear aldehydes and excellent conversions were achieved in the hydroformylation of alkenes. The hydroformylation reaction was applied to various olefinic substrates including the internal alkenes.
- Tijani, Jimoh,El Ali, Bassam
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p. 3492 - 3497
(2008/02/12)
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- High-precision catalysts: Regioselective hydroformylation of internal alkenes by encapsulated rhodium complexes
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We report the formation of high-precision catalysts using encapsulated rhodium complexes. In the current example, the encapsulated rhodium catalyst shows unprecedented high selectivity in the rhodium-catalyzed hydroformylation of internal alkenes, forming predominantly one of the branched aldehydes. This catalyst system is the first example that is able to discriminate between carbon atoms C3 and C4 in trans-3-octene. Copyright
- Kuil, Mark,Soltner, Theresa,Van Leeuwen, Piet W. N. M.,Reek, Joost N. H.
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p. 11344 - 11345
(2007/10/03)
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- Phosphabarrelenes as ligands in rhodium-catalyzed hydroformylation of internal alkenes essentially free of alkene isomerization
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Despite significant research efforts in the past, one of the remaining problems to be solved in industrially important hydroformylation is the chemoselective low-pressure hydroformylation of internal alkenes. We report here on a new class of phosphabarrelene/rhodium catalysts 2 that display very high activity towards hydroformylation of internal alkenes with an unusually low tendency towards alkene isomerization. Preparation of new phosphabarrelene ligands, studies of their coordination properties, as well as results obtained in the rhodium-catalyzed hydroformylation of cyclic and acyclic internal alkenes are reported.
- Fuchs, Evelyn,Keller, Manfred,Breit, Bernhard
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p. 6930 - 6939
(2007/10/03)
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- Hydroformylation of 1-octene in supercritical carbon dioxide and organic solvents using trifluoromethyl-substituted triphenylphosphine ligands
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Two different in situ prepared catalysts generated from Rh(CO) 2acac and trifluoromethyl-substituted triphenylphosphine ligands have been evaluated for their activity and selectivity in the hydroformylation of 1-octene. The solvents used were supercritical carbon dioxide, hexane, toluene, and perfluoromethylcyclohexane. The highest value for the turnover frequency, 9820 mol1-octene molRh-1 h-1, has been obtained in supercritical carbon dioxide using ligand I, P[C 6H3-3,5-(CF3)2]3. For both supercritical carbon dioxide and hexane employing ligand II, P(C 6H4-3-CF3)3, a selectivity towards the linear aldehyde product, nonanal, and an n:iso ratio of 79.3% and 4.6-4.8 have been obtained, respectively. These values are significantly higher than those obtained with triphenylphosphine as ligand (nonanal: 74-76%, n:iso: 3.1-3.3). An increase in trifluoromethyl substitution on the triphenyl ligand results in an increase in the 1-octene conversion rate, an increase in the n:iso ratio and a decrease in the overall selectivity towards aldehydes. In terms of turn-over frequency and selectivity the three ligands give comparable results in supercritical carbon dioxide and hexane. This leads to the conclusion that the properties of supercritical carbon dioxide as a solvent for hydroformylation can be better compared with those of hexane rather than with those of toluene.
- Koeken, Ard C. J.,Van Vliet, Michiel C. A.,Van Den Broeke, Leo J. P.,Deelman, Berth-Jan,Keurentjes, Jos T. F.
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p. 1553 - 1559
(2007/10/03)
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- Rhodium catalysed hydroformylation of alkenes using highly fluorophilic phosphines
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Highly fluorophilic phosphines incorporating at least one aromatic ring containing two directly attached perfluoroalkyl groups have been synthesised, their partition coefficients (organic phase : fluorous phase) measured and their electronic properties probed using 1JPtP data for their trans-[PtCl2L2] complexes. These phosphines have been used as modifying ligands for the rhodium catalysed hydroformylation of 1-octene in perfluorocarbon solvents. Catalyst activity, regioselectivity and the levels of rhodium leaching to the product phase vary with the substitution patterns of the modifying ligands that do not correlate with the electronic properties or partition coefficients of these ligands, but can be interpreted in terms of differences in the resting states of the catalysts. The Royal Society of Chemistry 2005.
- Adams, Dave J.,Bennett, James A.,Cole-Hamilton, David J.,Hope, Eric G.,Hopewell, Jonathan,Kight, Jo,Pogorzelec, Peter,Stuart, Alison M.
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p. 3862 - 3867
(2007/10/03)
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- Phenoxaphosphino-modified xantphos-type ligands in the rhodium-catalysed hydroformylation of internal and terminal alkenes
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The solubility of the modifying ligand is an important parameter for the efficiency of a rhodium-catalysed hydroformylation system. A facile synthetic procedure for the preparation of well-defined xanthene-type ligands was developed in order to study the influence of alkyl substituents at the 2-, and 7-positions of the 9,9-dimethylxanthene backbone and at the 2-, and 8-positions of the phenoxaphosphino moiety of ligands 1-16 on solubility in toluene and the influence of these substituents on the performance of the ligands in the rhodium-catalysed hydroformylation. An increase in solubility from 2.3 mmol·L-1 to > 495 mmol·L-1 was observed from the least soluble to the most soluble ligand. A solubility of at least 58 mmol·L-1 was estimated to be sufficient for a large-scale application of these ligands in hydroformylation. Highly active and selective catalysts for the rhodium-catalysed hydroformylation of 1-octene and trans-2-octene to nonanal, and for the hydroformylation of 2-pentene to hexanal were obtained by employing these ligands. Average rates of > 1600 (mol aldehyde) x (mol Rh)-1 x h-1 {conditions: p(CO/H 2) = 20 bar, T = 353 K, [Rh] = 1 mM, [alkene] = 637 mM} and excellent regio-selectivities of up to 99% toward the linear product were obtained when 1-octene was used as substrate. For internal olefins average rates of > 145 (mol aldehyde) x (mol Rh)-1 x h-1 {p(CO/ H2) = 3.6-10 bar, T = 393 K, [Rh] = 1 mM, [alkene] = 640-928 mM} and high regio-selectivities up to 91% toward the linear product were obtained.
- Bronger, Raymond P. J.,Bermon, Jochem P.,Herwig, Juergen,Kamer, Paul C. J.,Van Leeuwen, Piet W. N. M.
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p. 789 - 799
(2007/10/03)
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- Phosphabarrelene-rhodium complexes as highly active catalysts for isomerization free hydroformylation of internal alkenes
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A new class of phosphabarrelene-rhodium catalysts is described which allows for the first time hydroformylation of internal alkenes with very high activity and which proceeds essentially free of alkene isomerization.
- Breit, Bernhard,Fuchs, Evelyn
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p. 694 - 695
(2007/10/03)
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- Syntheses and coordination behaviour of 2-(ortho-phosphinophenyl)-functionalised 1,3-dioxolanes and 1,3-dioxanes towards a [(COD)Rh]-complex fragment - Models for immobilised complexes
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The syntheses are reported of the ether-phosphine ligands: 2-(ortho-diphenylphosphinophenyl)-1,3-dioxolane (1a), 2-(ortho-diisopropylphosphinophenyl)-1,3-dioxolane (1b), 2-(ortho-diphenylphosphinophenyl)-1,3-dioxane (1c), 2-(ortho-diisopropylphosphinophenyl)-1,3-dioxane (1d). Their reaction with [(COD)RhCl]2 (COD: 1,5-cyclooctadiene) results in the formation of the mononuclear complexes: {chloro(COD)[2-(ortho-diphenylphosphinophenyl)-1,3-dioxolane]rhodium(I)} (2a), {chloro(COD)[2-(ortho-diisopropylphosphinophenyl) -1,3-dioxolane]rhodium(I)} (2b), {chloro(COD)[2- (ortho-diphenylphosphinophenyl)-1,3-dioxane]rhodium(I)} (2c), and {chloro(COD)[2-(ortho-diisopropylphosphinophenyl)-1,3-dioxane]rhodium(I)} (2d). The chloride ligands of compounds 2a and 2b were abstracted with TlPF6, with accompanied insertion of an acetal oxygen atom of the ligands 1a and 1b into the coordination sphere of the metal centre, producing {(COD)[η2-P,O-2-(ortho-diphenylphosphinophenyl) -1,3- dioxolane]rhodium(I)}PF6 (3a*PF6) and {(COD)[η2-P,O-2-(ortho-diisopropylphosphinophenyl)-1,3- dioxolane]rhodium(I)}PF6 (3b*PF6). In contrast the dioxane analogues of 3, 3c*BF4 and 3d*BF4, were formed by reacting the ligands 1c, 1d with [Rh(COD)2]BF4. The ligands 1 and the complexes 2 serve as model compounds for their via acetalation to a polyvinylalcohol resin bound analogues. The complexes synthesised were employed as pre-catalysts in the hydroformylation reaction of 1-octene.
- Ahlmann,Walter, Olaf
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p. 3117 - 3131
(2007/10/03)
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- Hydroformylation with unmodified rhodium catalysts in supercritical carbon dioxide
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The present invention relates to processes for the preparation of oxo products by the hydroformylation of substrates having C═C double bonds using unmodified rhodium catalysts in a reaction mixture essentially consisting of the substrates, the catalyst and carbon dioxide in a supercritical state (scCO2). In particular, the invention relates to such processes for the preparation of products which contain substantial proportions of branched i-oxo products. Further, the invention relates to such processes for the hydroformylation of substrates which do not correspond to the general formula CnH2n. The invention further relates to such processes in which the separation of product and catalyst is effected using the special solvent properties of scCO2.
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Page column 5-7
(2008/06/13)
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- Hydroformylation of higher olefins by rhodium/tris-((1H,1H,2H,2H-perfluorodecyl)phenyl)phosphites complexes in a fluorocarbon/hydrocarbon biphasic medium: Effects of fluorinated groups on the activity and stability of the catalytic system
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The synthesis of three fluorous triarylphosphites in which an 'insulating' ethylene segment separates the perfluoroalkylgroup from the aryl group is described. The stabilities, solubilities and partition coefficients of these new compounds are reported. The complexes generated in situ from these fluorous triarylphosphites and Rh(acac)(CO)2 have been tested as catalysts for the hydroformylation of various olefins under fluorous biphasic conditions. The activities and the selectivities were found to vary markedly with the position of the perfluoroalkylgroup on the aromatic ring. The possibility to recover the catalytic system was also investigated from consecutive recycling experiments.
- Mathivet, Thomas,Monflier, Eric,Castanet, Yves,Mortreux, André,Couturier, Jean-Luc
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p. 3877 - 3888
(2007/10/03)
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- Hydroformylation in perfluorinated solvents; improved selectivity, catalyst retention and product separation
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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.
- Foster, Douglas F,Gudmunsen, David,Adams, Dave J,Stuart, Alison M,Hope, Eric G,Cole-Hamilton, David J,Schwarz, Gary P,Pogorzelec, Peter
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p. 3901 - 3910
(2007/10/03)
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- New version of the TEMPO-based catalytic system for the oxidation of alcohols to aldehydes
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A new chemoselective catalytic system for the title oxidation was developed using methyltrioxorhenium (3 mol%), KBr (10 mol%) and TEMPO (3 mol%) as co-catalysts and Oxone as a terminal oxidant.
- Kowalczyk,Skarzewski
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p. 1413 - 1417
(2007/10/03)
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- Rhodium-catalyzed biphasic hydroformylation of 4-octene using water-soluble calix[4]arene-phosphine ligands
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The hydroformylation of water-insoluble internal olefins has been realized in biphasic systems via the use of rhodium complexes of water-soluble calix[4]arene-phosphines. This catalytic system resulted in a good level of activity and reusability.
- Shirakawa,Shimizu,Sasaki
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p. 777 - 779
(2007/10/03)
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- Synthesis of sulfated mono- and ditertiary phosphines, complex chemistry and catalysis
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Cyclic and bicyclic sulfates have been prepared from commonly available alcohols. Nucleophilic cleavage of the cyclic sulfates affords a new type of water-soluble mono- and ditertiary phophines bearing -OSO3Li groups in distinguished positions in the molecular framework. Both phosphines have amphiphilic character. Reactions of the chiral 2 and the dppp analogue 5 with [Rh(COD)Cl]2 and Pt(PhCN)2Cl2 provide novel zwitterionic complexes. Rhodium complexes of 2 and 5 have been successfully applied in liquid biphasic hydroformylation of styrene and octene-1. When the rhodium complex of 5 was used as catalyst in hydroformylation of styrene, less then 4 ppm rhodium could be detected in the organic phase.
- Gulyas,Dobo,Bakos
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p. 1040 - 1048
(2007/10/03)
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- Phosphabenzenes as monodentate π-acceptor ligands for rhodium-catalyzed hydroformylation
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A new class of phosphinine/rhodium catalysts for the hydroformylation of terminal and internal alkenes is presented in this study. A series of phosphabenzenes 1-14 has been prepared by condensation of phosphane or tris(trimethylsilyl)phosphane with the corresponding pyrylium salt. Trans[(phosphabenzene)2RhCl(CO)] complexes 21-25 have been prepared and studied spectroscopically and by X-ray crystal-structure analysis, The hydroformylation of oct-1-ene has been used to identify optimal catalyst preformation and reaction conditions. Hydroformylation studies with 15 monophosphabenzenes have been performed. The catalytic performance is dominated by steric influences, with the phosphabenzene 8/rhodium system being the most active catalyst. Turnover frequencies of up to 45370 h-1 for the hydroformylation of oct-1-ene have been determined. In further studies, hydroformylation activity toward more highly substituted alkenes was investigated and compared with the standard industrial triphenylphosphane/rhodium catalyst. The reactivity differences between the phosphabenzene and the triphenylphosphane catalyst increase on going to the more highly substituted alkenes. Even tetra substituted alkenes reacted with the phosphabenzene catalyst, whereas the triphenylphosphane system failed to give any product. In situ pressure NMR experiments have been performed to identify the resting state of the catalyst. A monophosphabenzene complex [(phosphinine 8)Ir(CO)3H] could be detected as the predominant catalyst resting state.
- Breit, Bernhard,Winde, Roland,Mackewitz, Thomas,Paciello, Rocco,Harms, Klaus
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p. 3106 - 3121
(2007/10/03)
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- Synthesis of new Calix[4] arene-based phosphorus ligands and their application in the Rh(l) catalyzed hydroformylation of 1-octene
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The synthesis of calix[4]arene-based phosphorus diamides and phosphites is described. These oligocyclic ligands have been tested in the Rh(I)-catalyzed hydroformylation of 1-octene. Depending on the reaction conditions, yields up to 99% and n/iso-selectivities between 0.7 and 2.6 have been observed. tert-Butyl groups on the upper rim of the calix[4]arene template had a beneficial effect on the catalytic reaction. In general biuret-derived P-ligands were superior. For comparison, the corresponding "monomeric" ligands have also been synthesized and were employed in the catalytic reaction.
- Kunze,Selent,Neda,Schmutzler,Spannenberg,Boerner
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p. 577 - 585
(2007/10/03)
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- Novel oxyfunctionalized phosphonite ligands for the hydroformylation of isomeric n-olefins
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Industrially relevant selectivities and turnover frequencies of up to 18710 h-1 are achieved with novel 2,2'-dihydroxybiphenyl phosphonite ligands such as 1 in the rhodium-catalyzed hydroformylation of internal octenes. R1 = H, alkyl; R2 = OMe, tBu.
- Selent, Detlef,Wiese, Klaus-Diether,Roettger, Dirk,Boerner, Armin
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p. 1639 - 1641
(2007/10/03)
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- Rhodium and palladium complexes from 1,1′ and 1,2 ferrocenylphosphine as bidentate ligands. Versatile coordination
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The complexation of the mixed bidentate ligands 1-diphenylphosphino-1′-diphenylthiophosphinoferrocenyl and 1,2-bis-(diphenylphosphino)ferrocenyl with rhodium(I) and palladium(II) species yield a range of mono- and dirhodium or palladium complexes. Their interest as possible catalysts for alkene hydroformylation and alkoxycarbonylation and Heck coupling reactions has been assessed. Fe[C5Me4P(S)Ph2][C5Me 4PPh2]PdCl2 and Fe[C5H2-1,2-(PPh2)2-4- tBu][C5H5]PdCl2 have been characterized by single-crystal X-ray diffraction studies.
- Broussier, Roland,Bentabet, Emmanuelle,Laly, Myriam,Richard, Philippe,Kuz'mina, Lyudmila G.,Serp, Philippe,Wheatley, Nigel,Kalck, Philippe,Gautheron, Bernard
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- A new route for the synthesis of amphiphilic and water-soluble ligands: Monoand di-tertiary phosphines having an alkylene sulfate chain
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Cyclic sulfates react with LiPPh2 to form a series of new amphiphilic or water-soluble ligands: monotertiary phosphines with one or two alkylene sulfate chains and ditertiary phosphines with one or two hydrophilic tails attached to bridgehead carbon atom; the application of zwitterionic RhI complexes (sulfatephos)2Rh(cod) and (sulfatediphos)Rh(cod) in liquid biphasic catalysis has been demonstrated for the hydroformylation of styrene and oct-1-ene.
- Gulyas, Henrik,Arva, Peter,Bakos, Jozsef
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p. 2385 - 2386
(2007/10/03)
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- Photochemical Hydroformylation with Cobalt Catalysts in Methanol
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The photochemical hydroformylation of 1-octene with cobalt/phosphane complexes in methanol leads under mild conditions (80 deg C, 80 bar CO/H2) with >= 90percent selectivity to linear aldehydes.The reaction rate increases with temperature (Ea = 5 - 6 kcal/mol) and synthesis gas pressure, and is nearly independent of the cobalt source, e.g.Co(OAc)2, Co2(CO)8, or Co2(CO)6(PBu3)2.At low pressures hydroesterification is the preferred photoreaction of 1-octene.Isoprene reacts under similar conditions to give unsaturated oxoproducts and linear isoprene dimers.With unmodified octacarbonyldicobalt the hydroformylation of internal olefins is enhanced by UV light, but not the reaction of terminal olefins or dienes.UV irradiation of cobalt acetate under hydroformylation conditions leads to rapid reduction of the Co(II) species, thus decreasing the induction period from ca. 15 h (without irradiation) to ca. 30 min.
- Mirbach, Manfred J.,Topalsavoglou, Nikolaos,Phu, Tuyet Nhu,Mirbach, Marlis F.,Saus, Alfons
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p. 1422 - 1440
(2007/10/02)
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