Regioselective Hydroformylation of Alkenes Catalyzed by Di(n-carboxylato)rhodium(I) Complexes

Doyle, Michael P.; Shanklin, Michael S.; Zlokazov, M. V.

doi:10.1055/s-1994-22946

Cited by 21 publications

(3 citation statements)

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“…We like to mention briefly that the high n -regioselectivity with 96.7% originates from the steric hindrance of the substrate 3,3-dimethyl-1-butene. This has been already discussed for modified and unmodified rhodium catalysts . The high chemoselectivity for the alkane with 15.5% is a serious problem using nonpolar solvents.…”

Section: Results and Discussionmentioning

confidence: 79%

Investigation into the Equilibrium of Iridium Catalysts for the Hydroformylation of Olefins by Combining In Situ High-Pressure FTIR and NMR Spectroscopy

et al. 2014

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A detailed quantitative study of phosphine-modified hydrido iridium complexes relevant for the hydroformylation reaction has been performed using HP-FTIR and HP-NMR spectroscopy. The equilibrium composition under typical reaction conditions has been characterized. Investigation of the temperature dependency allowed even for a distinction between both configurational isomers of [HIr(CO)2(PPh3)2]. The trihydride complex [H3Ir(CO)(PPh3)2] is part of the investigated equilibrium depending on the ratio of p(H2)/p(CO). Single rate constants for the sequence of corresponding equilibrium reactions have been estimated from stopped-flow experiments and conventional measurements, monitoring the concentrations after changing reactant concentrations.

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Section: Results and Discussionmentioning

confidence: 79%

Investigation into the Equilibrium of Iridium Catalysts for the Hydroformylation of Olefins by Combining In Situ High-Pressure FTIR and NMR Spectroscopy

et al. 2014

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“…The comparison of the hydroformylation reaction of styrene is somewhat difficult to make because of different conditions used (Supporting Information), 2d,4c,5c,− but it indicates that the species 6a , b , c and 10a , b , c are good catalysts. Compounds 6a and 10a are the best in this series, in particular in comparison with the second best catalyst for this substrate (Pydiphos/Rh(CO) 2 (acac)).…”

Section: Resultsmentioning

confidence: 99%

“…H} NMR (CD2Cl2) -1 33. (d, Pcalix, JP-Rh ) 144), -141.02 (septuplet, PF6 -, JP-F ) 711); MS (MALDI-TOF) 815 (10%, (CalixP2)Rh), 831 (70%, (CalixP(O)P)Rh) 939 (15%, (CalixP-(O)P)Rh(COD)) 1560 (50%, (CalixP(O)P)2Rh).…”

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confidence: 99%

Syntheses and Characterization of Upper Rim 1,2- and 1,3-Diphosphinated Calix[4]arenes and Their Corresponding 1,5-Cyclooctadienylrhodium(I) Complexes: Comparison of the Catalytic Hydroformylation Properties of Terminal Alkenes

et al. 2003

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The 5,11- (1,2-isomer) and 5,17-bis(dialkylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene (1,3-isomer) ligands (alkyl = Me, i-Pr) have been prepared and coordinated to Rh(COD)+ fragments (COD = 1,5-cyclooctadiene). The ligands 5,17-bis(diphenylphosphino)-11,23-dibromo-25,26,27,28-tetra-n-propoxycalix[4]arene and 5,11-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene have been coordinated to M(COD)+ (M = Rh, Ir) and RhCl(CO) fragments, as well. On the basis of mass spectrometry and 31P NMR spin−lattice relaxation time measurements (T 1), all of the complexes are found to be dimers. Molecular modeling provides evidence that ring stress favors the dimer over the monomer, and the modeled structures for both 1,2- and 1,3-isomers have been corroborated by the comparison of the photophysics of the Ir(COD)+ species at 77 K. The decrease in emission lifetimes of the P2Ir(CC)2 + lumophore in the presence of 1-hexene is more pronounced for the 1,3-isomer, indicating reduced steric hindrance about the metallic center. The catalytic hydroformylation of five terminal alkenes using all six Rh(COD)+ catalyst precursors has been investigated under various conditions in order to extract the turnover frequencies (tof as defined as the number of moles of products divided by the total number of moles of rhodium used per hour) and the ratios of the product distribution (n/ i, normal vs internal). The comparison of the data suggests that the basicity and the cone angle of the phosphines influence the n/i ratios. The tof's are generally larger for the 1,2-series for 1-hexene, but depend on the nature of the phosphine for styrene, vinyl acetate, vinyl benzoate, and vinyl p-tert-butylbenzoate. All in all, these complexes are good catalysts with respect to literature data, notably those containing the (i-Pr2P)− groups. During the course of this study, one hydride carbonyl complex has been synthesized and characterized from 1H and 31P NMR, IR, and T 1 measurements.

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The Hydroformylation Reaction

et al. 2000

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The reaction of 1‐alkenes with carbon monoxide and hydrogen in the presence of a catalyst gives the corresponding homologous aldehydes. The discovery of this reaction was made by Roelen in 1938 using Co 2 (CO) 8 as the catalyst at high temperature (120–170°) and high pressure of carbon monoxide/hydrogen (200–300 bar). This reaction has been called the “Oxo reaction”, “Roelen reaction” or “hydroformylation”. Hydroformylation is a general term indicating that both a hydrogen and a formyl group are introduced to unsaturated bonds, especially olefins. Later this reaction was developed as an industrial process, i.e., the Oxo Process, for the production of alkanals from 1‐alkenes using a cobalt or rhodium catalyst. Most noteworthy is the conversion of propene to butanal, which can be subsequently hydrogenated to 1‐butanol or converted to 2‐ethylhexanol by self‐aldol condensation. 2‐Ethylhexanol, a crucial intermediate for the production of ester‐type plasticizers, is the most important bulk chemical produced by the Oxo Process. A variety of transition metal catalysts other than Co 2 (CO) 8 have been investigated, including phosphine complexes of cobalt and hydridocobalt clusters. Platinum and ruthenium complexes show reasonably good catalytic activities, but modified cobalt catalysts are still much more advantageous. However, various rhodium complexes demonstrate higher catalytic activity (10 3 –10 4 times) than the cobalt complexes. Although the price of rhodium is higher than cobalt, reactions using rhodium catalysts require lower temperature (50–80°) and pressure (10–50 atm). Other important commercial applications of hydroformylation include the production of long‐chain alcohols from C 5 –C 17 isomeric linear alkenes. These long‐chain alcohols serve as intermediates for lubricants, plasticizers and detergents. The hydroformylation of ethene to propanal is another important Oxo Process. In this chapter, the authors put clear emphasis on the scope of the hydroformylation reaction in organic synthesis. In this context, there is a relevant review in 1987 of the hydroformylation of functionalized alkenes. The hydroformylation reaction now can be performed under very mild conditions using a variety of functionalized alkenes. Reactions in aqueous biphase, supercritical carbon dioxide or fluorous biphase have recently emerged in response to separation and environmental issues. In fact, a highly efficient Oxo Process using a water‐soluble rhodium catalyst in aqueous biphasic conditions has been commercialized by Ruhrchemie/Rhône‐Poulenc for the production of butanal. Asymmetric hydroformylation of prochiral olefins catalyzed by enantiopure rhodium complexes has been developed to the level that practical applications appear possible. Although the reactions of formaldehyde, oxiranes, and others with carbon monoxide and hydrogen in the presence of transition metal catalyst could be considered as variations of hydroformylation, this chapter only deals with hydroformylation of carbon‐carbon multiple bonds.

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Regioselective Hydroformylation of Alkenes Catalyzed by Di(n-carboxylato)rhodium(I) Complexes

Cited by 21 publications

References 0 publications

Investigation into the Equilibrium of Iridium Catalysts for the Hydroformylation of Olefins by Combining In Situ High-Pressure FTIR and NMR Spectroscopy

Investigation into the Equilibrium of Iridium Catalysts for the Hydroformylation of Olefins by Combining In Situ High-Pressure FTIR and NMR Spectroscopy

Syntheses and Characterization of Upper Rim 1,2- and 1,3-Diphosphinated Calix[4]arenes and Their Corresponding 1,5-Cyclooctadienylrhodium(I) Complexes: Comparison of the Catalytic Hydroformylation Properties of Terminal Alkenes

The Hydroformylation Reaction

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