Carbon Monoxide and Synthesis Gas Chemistry: Hydroformylation (Oxo Synthesis, Roelen Reaction)

Frohning, C.‐D.; Kohlpaintner, Christian W.; Gauß, M.; Seidel, Andreas; Pf, Torrence; Heymanns, P.; Höhn, Anton; Beller, Matthias; Knifton, John F.; Klausener, Alexander; Jentsch, J.‐D.; Tafesh, Ahmed

doi:10.1002/9783527619351.ch2a

Cited by 26 publications

(8 citation statements)

References 507 publications

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“…Hydroformylation is one of the largest industrial homogeneous catalytic processes in the world, producing more than 6,000,000 tons of aldehydes each year . In this process, alkenes react with hydrogen and carbon monoxide to give either linear or branched aldehydes (Scheme ; R = alkyl).…”

Section: Introductionmentioning

confidence: 99%

Comprehensive Theoretical Study on the Mechanism of Regioselective Hydroformylation of Phosphinobutene Catalyzed by a Heterobinuclear Rhodium(I)−Chromium Complex

Tang

Qin

et al. 2006

Organometallics

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A concerted mechanism for the hydroformylation of phosphinobutene catalyzed by the heterobinuclear complex (CO)4Cr(μ-PH2)2RhH(CO)(PH3) was elucidated by density functional theory (DFT), with particular emphasis on the catalytic cycle, the regioselectivity, the cooperativity of Cr with Rh, and the interpretation of experimental observations. Four possible mechanisms were investigated, and the results were compared. It is found that the introduction of the Cr(CO)4 moiety remodels the mechanism. The Rh−Cr-catalzyed hydroformylation mechanism includes the following: (a) formation of the chelate acyl species through a chelate associative mechanism including olefin addition, olefin insertion, and carbonyl insertion steps, (b) CO addition to the chelate acyl species with the formation of a monodentate acyl species, and (c) the conversion of the monodentate acyl species to the product aldehyde through H2 coordination, H2 oxidative addition, and aldehyde elimination. Carbonyl insertion is predicted to be the rate-limiting step, with a free energy barrier of 86.76 kJ/mol in benzene solution at 353.15 K and 27.15 atm. The favorability of the branched product is predicted to be nearly 100% both kinetically and thermodynamically. The chromium serves as an orbital reservoir in olefin addition and insertion steps via the variation of the orbital interaction between Rh and Cr atoms. The catalytic activity of the Rh(I)−Cr bimetallic complex is higher than that of the monometallic Rh catalysts. These could explain satisfactorily the reported experimental observations.

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Section: Introductionmentioning

confidence: 99%

Comprehensive Theoretical Study on the Mechanism of Regioselective Hydroformylation of Phosphinobutene Catalyzed by a Heterobinuclear Rhodium(I)−Chromium Complex

Tang

Qin

et al. 2006

Organometallics

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“…Metal-catalyzed carbonylation is a versatile synthetic method for a broad spectrum of organic carbonyl compounds − Along this line, we have focused our research on the carbonylative polymerization − and demonstrated the feasibility of synthesizing poly(β-alanine) and its derivatives via CO−aziridine alternating copolymerization .…”

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confidence: 99%

Novel Cobalt-Catalyzed Carbonylation of 2-Aryl-2-oxazolines

2003

Org. Lett.

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“…oxo synthesis) has become one of the most important industrial processes, having an annual production of aldehydes approaching 10 million tons (1)(2). Hydrofomylation involves the addition of syngas to an alkene to produce aldehydes in a reaction that exhibits perfect atom economy (Scheme 1).…”

Section: Hydroformylation Of Higher Olefinsmentioning

confidence: 99%

Hydroformylation in CO₂-Expanded Media

Wang

Cai

Jin

et al. 2009

Gas-Expanded Liquids and Near-Critical Media

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Carbon Monoxide and Synthesis Gas Chemistry: Hydroformylation (Oxo Synthesis, Roelen Reaction)

Cited by 26 publications

References 507 publications

Comprehensive Theoretical Study on the Mechanism of Regioselective Hydroformylation of Phosphinobutene Catalyzed by a Heterobinuclear Rhodium(I)−Chromium Complex

Comprehensive Theoretical Study on the Mechanism of Regioselective Hydroformylation of Phosphinobutene Catalyzed by a Heterobinuclear Rhodium(I)−Chromium Complex

Novel Cobalt-Catalyzed Carbonylation of 2-Aryl-2-oxazolines

Hydroformylation in CO₂-Expanded Media

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Carbon Monoxide and Synthesis Gas Chemistry: Hydroformylation (Oxo Synthesis, Roelen Reaction)

Cited by 26 publications

References 507 publications

Comprehensive Theoretical Study on the Mechanism of Regioselective Hydroformylation of Phosphinobutene Catalyzed by a Heterobinuclear Rhodium(I)−Chromium Complex

Comprehensive Theoretical Study on the Mechanism of Regioselective Hydroformylation of Phosphinobutene Catalyzed by a Heterobinuclear Rhodium(I)−Chromium Complex

Novel Cobalt-Catalyzed Carbonylation of 2-Aryl-2-oxazolines

Hydroformylation in CO2-Expanded Media

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Hydroformylation in CO₂-Expanded Media