Hydroformylation with a Rhodium/Bulky Phosphite Modified Catalyst. A Comparison of the Catalyst Behavior for Oct-1-ene, Cyclohexene, and Styrene

Abstract

Hydroformylation with a rhodium/bulky phosphite modified catalyst. A comparison of the catlyst behaviour for oct-1-ene, cyclohexene and styrene van Rooy, A.; Kamer, P.C.J.; van Leeuwen, P.W.N.M. Published in: Organometallics DOI:10.1021/om00001a010Link to publication Citation for published version (APA):van Rooy, A., Kamer, P. C. J., & van Leeuwen, P. W. N. M. (1995). Hydroformylation with a rhodium/bulky phosphite modified catalyst. A comparison of the catlyst behaviour for oct-1-ene, cyclohexene and styrene. Organometallics, 14, 34. DOI: 10.1021/om00001a010 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. The rhodium-catalyzed hydroformylation of oct-1-ene, cyclohexene, and styrene has been studied using Rh( C0)Acac as the catalyst precursor and tris(2-tert-butyl-4-methylphenyl) phosphite as the ligand (2' = 40-100 "C, PCO = 2.5-44 bar, PHZ = 2.5-50 bar, toluene as a solvent). For oct-1-ene, very high hydroformylation rates are obtained (39.8 x lo3 mol [mol Rhl-l h-l) under mild conditions (PCO = 10 bar, PHZ = 10 bar, T = 80 "C). The concentration dependencies of the reaction rate show that the rate-determining step is the reaction of HZ with the acylrhodium complex. A negative order in the CO concentration is observed. For cyclohexene, the reaction rate is lower under the same conditions (512 mol [mol Rhl-I h-l, [cyclohexene] = 0.91 M), the addition of cyclohexene to the starting rhodium hydride complex now being rate-limiting. In the hydroformylation of styrene, the rate is 3 times lower than that of oct-1-ene. For the formation of the linear 3-phenylpropanal, the rate-determining step is the reaction of Hz with the rhodium acyl species. CO inhibits the reaction. In contrast with the formation of the secondary 2-octyl species from oct-1-ene, the formation of the secondary (1-phenylethy1)rhodium species is reversible. For the formation of the branched aldehyde, the kinetics depend strongly on the CO partial pressure. At low CO pressures, addition of CO to the proposed (y3-l-phenylethyl)rhodium intermediate is slow. At higher CO pressures, hydrogenolysis of the rhodium acyl intermediate is the rate-determining step and the rate decreases with increasing CO. IntroductionMuch research has been conducted to elucidate the mechanism and the kinetics of the rhodium-ca...

The crystal structure of carbonyl-[4-(2,4-dichlorophenylamino)pent-3-en-2-onato-κ2 N,O]-(triphenylphosphine-κP)rhodium(I), RhC30H25Cl2NO2P

“…containing chelating mono-anionic bidentate (L,L′) ligands coordinated to rhodium via (O,O) donor atoms have been studied as catalyst precursors [1][2][3]. The title complex forms part of a study which investigates complexes containing 2 ]-type complex will be substituted by triphenyl phosphine, with the product being one of two possible isomers [5], has been confirmed [6][7][8].…”

Crystal structure of carbonyl-(4-(2,6-dichlorophenylamino)pent-3-en-2-onato-κ2N,O)-(triphenylphosphine-κP)-rhodium(I) acetone solvate, C31.5H28Cl2NO2.5PRh

“…containing chelating mono-anionic bidentate (L,L') ligands coordinated to rhodium via (O,O') donor atoms have been studied extensively as catalyst precursors [1][2][3]. In this study the investigation of such structures is followed up by complexes containing bidentate enaminoketonate ligands such as 4-(phenylamino)pent-3-en-2-onate [4] …”

Rh-catalyzed linear hydroformylation of styrene

“…Therefore, the coordination of CO (3a to 4a) is very fast. 8 Here we report a group of π-accepting bidentate phosphorus ligands in the selective Rh-catalyzed styrene hydroformylation reaction and the tunability of the reaction outcome either to the branched or to the linear aldehyde. used binaphthol-based diphosphites in the hydrocyanation of styrene towards the linear product.…”