Novel active dirhodium complexes for the low pressure hydroformylation reaction. Unexpected inhibiting effect of high partial pressures of hydrogen

Kalck, Philippe; Pérès, Yolande; Quéau, R.; Molinier, J.; Escaffre, P.; Oliveira, Edson Leandro de; Peyrille, Bruno

doi:10.1016/0022-328x(92)83173-f

Cited by 13 publications

(3 citation statements)

References 2 publications

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“…When the pressure is released, the dinuclear compounds [Rh 2 (μ-thiolate) 2 (CO) 4 (PPh 3 ) 2 ] are re-formed in solution. 5c,9c,12a …”

Section: Resultsmentioning

confidence: 99%

“…This result is in accordance with the presence of a mononuclear rhodium hydride catalyst. If the reaction mechanism involved dinuclear species,5c only dideuterated alcohols or dihydrogenated alcohols would be expected. In a separate experiment we tried to observe the putative dihydrido−dirhodium intermediate.…”

Section: Resultsmentioning

confidence: 99%

“…Kalck et al described the advantages of using dinuclear bridged rhodium thiolate complexes as catalyst precursors in the hydroformylation reaction . A catalytic cycle, based on spectroscopic evidence and theoretical calculations, in which the dinuclear framework is retained for all steps has been proposed for [Rh 2 (μ-SR) 2 (CO) 2 (PR 3 ) 2 ] precursors.…”

Section: Introductionmentioning

confidence: 99%

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High-Pressure Infrared Studies of Rhodium Complexes Containing Thiolate Bridge Ligands under Hydroformylation Conditions

Diéguez¹,

Claver²,

Masdeu-Bultó³

et al. 1999

Organometallics

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In situ high-pressure IR spectroscopy studies of the rhodium catalyst systems [Rh2{μ-S(CH2)3N(Me2)}2(COD)2]/PR3 (R = Ph, OPh), [Rh2{μ-S(CH2)2S}(COD)2]/PPh3, [Rh2{μ-S(CH2)4S}(COD)2]2/PPh3, [Rh2{μ-XANTOSS}(COD)2]2/PPh3, and [Rh(acac)(CO)2]/PR3 (R = Ph, OPh) revealed the presence of mononuclear rhodium hydride species under hydroformylation conditions (80 °C, 5−30 bar). The activities and selectivities, obtained during the hydroformylation of 1-hexene using these systems as catalyst precursors, can be fully accounted for by the mononuclear species observed. Deuterioformylation experiments using dinuclear [Rh2{μ-S(CH2)3N(Me2)}2(COD)2]/PR3 systems lent no support to a dinuclear mechanism.

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“…When the pressure is released, the dinuclear compounds [Rh 2 (μ-thiolate) 2 (CO) 4 (PPh 3 ) 2 ] are re-formed in solution. 5c,9c,12a …”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

High-Pressure Infrared Studies of Rhodium Complexes Containing Thiolate Bridge Ligands under Hydroformylation Conditions

Diéguez¹,

Claver²,

Masdeu-Bultó³

et al. 1999

Organometallics

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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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Binuclear Cooperative Catalysts for the Hydrogenation and Hydroformylation of Olefins

et al. 2013

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Cooperative activation of substrates simultaneously by a (transition) metal and a protein residue is a common strategy in enzyme catalysis. Cooperative dinuclear catalysis for synthetic systems is relatively underdeveloped. Here, we focus on some examples of dinuclear hydrogenation and hydroformylation reactions, with the aim to stimulate the scientific community to develop more catalytic processes based on cooperative dinuclear systems.

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Novel active dirhodium complexes for the low pressure hydroformylation reaction. Unexpected inhibiting effect of high partial pressures of hydrogen

Cited by 13 publications

References 2 publications

High-Pressure Infrared Studies of Rhodium Complexes Containing Thiolate Bridge Ligands under Hydroformylation Conditions

High-Pressure Infrared Studies of Rhodium Complexes Containing Thiolate Bridge Ligands under Hydroformylation Conditions

The Hydroformylation Reaction

Binuclear Cooperative Catalysts for the Hydrogenation and Hydroformylation of Olefins

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