Evidence of colloidal rhodium formation during the biphasic hydroformylation of 1-octene with thermoregulated phase-transfer phosphine rhodium(I) catalyst

Wen, Fei; Bönnemann, Helmut; Jiang, Jingyang; Lu, Dongmei; Wang, Yanhua; Zhang, Jin

doi:10.1002/aoc.838

Cited by 34 publications

(14 citation statements)

References 55 publications

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“…These nanoparticles tend to ripening behaviour during the recycling runs which finally leads to precipitation and deactivation of the catalyst. [33] 4 Soluble Polymer-Bound Catalysts…”

Section: Thermoregulated Phase-transfer Catalystsmentioning

confidence: 99%

Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

2006

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Considerable effort has been done to overcome the loss of catalyst in homogeneously catalysed processes. In this contribution we describe five recycling concepts for thermoregulated catalyst separation and recycling: fluorous biphasic systems (FBS), thermoregulated phase transfer catalysis (TRPTC), soluble polymer-based catalysis, thermoregulated microemulsions and temperature-dependent multicomponent solvent systems (TMS). Each of these concepts has its own special advantages like low catalyst leaching or simple process engineering but also drawbacks like usage of expensive special solvents or complex and expensive catalysts. In this context, TMS systems exhibit most advantages of the other concepts combined with the possibility to use common and cheap solvents as well as numerous classical molecular catalysts. Therefore, TMS systems are expected to be one of the most promising thermomorphic recycling concepts for industrial scale.

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“…These nanoparticles tend to ripening behaviour during the recycling runs which finally leads to precipitation and deactivation of the catalyst. [33] 4 Soluble Polymer-Bound Catalysts…”

Section: Thermoregulated Phase-transfer Catalystsmentioning

confidence: 99%

Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

2006

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“…[8] Investigations by Bönnemann et al of 1-octene hydroformylation in an aqueous biphasic system with a rhodium colloid stabilized by oligo(ethylene glycol)-substituted phosphine show that the catalytic reaction is insensitive to the mercury test probing for heterogeneous catalysis, overall this study concludes that the nature of the active sites is unclear to date and does not further comment the mechanism of catalysis. [9] It is generally recognized that hydroformylation can occur by Rh I species. Rh 0 compounds can be converted to Rh I by oxidative addition of hydrogen.…”

Section: Introductionmentioning

confidence: 99%

Hydroformylation with Dendritic‐Polymer‐Stabilized Rhodium Colloids as Catalyst Precursors

Tuchbreiter

Mecking

2007

Macro Chemistry & Physics

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Hydroformylation of 1‐hexene with rhodium colloids stabilized by poly(ethylene imine) amides with a hyperbranched polyamine core and a lipophilic periphery is reported. The catalyst selectivity for aldehydes increases with increasing temperature or pressure. The ratio of linear to branched aldehydes decreases with increasing temperature. At 80 °C and 90 atm, 1‐hexene is converted completely with 96% selectivity for aldehydes, with a ratio of linear/branched aldehydes of 58:42. Turnover numbers up to 3 × 104 (calculated with respect to the entire amount of Rh present) were observed. The results indicate that the catalyst precursor colloids serve as a reservoir for the formation of soluble Rh(I) complexes as the active species.magnified image

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“…Moreover, B ö nnemann et al [75] have proved the in situ formation of Rh colloids when such a catalyst was applied to the aqueous biphasic hydroformylation of 1 -octene.…”

Section: Hydroformylation Of Olefi Nsmentioning

confidence: 99%

Rhodium and Ruthenium Nanoparticles in Catalysis

Roucoux¹,

Nowicki²,

Philippot³

2007

Nanoparticles and Catalysis

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IntroductionThe last decade has evidenced an ever -increasing interest in the nanometric size chemical species area. More particularly, a great number of studies have been based on the synthesis and applications of noble transition metal colloids [1,2] . The development of soluble metal nanoparticles and colloids as highly active nanocatalysts has been the focus of considerable effort and several research groups have contributed signifi cantly to this central fi eld of nanosciences and nanotechnology [3 -5] . Due to their particular matter state, between homogeneous and heterogeneous, these frontier species are sometimes called " semi -heterogeneous " or " nanoheterogeneous " catalysts. From now on, soluble noble metal nanoparticles are considered as an unavoidable family of catalysts under mild conditions [6 -10] .Contrary to classical heterogeneous catalysts, metal nanocatalysts -generally defi ned as particles between 1 and 10 nm in size -can be obtained by the bottomup approach in two strategic ways according to the nature of the precursor, namely metal salts and organometallic compounds. Moreover, noble metal nanoparticles can be synthesized by a variety of methods according to the " organic " or " aqueous " nature of the media and the type of stabilizers used. The choice of the reaction parameters can provide some degree of control of particle size and particle composition, which is important for high activity and selectivity in catalytic applications. Finally, this fi eld has also allowed, from recent kinetic and mechanistic studies, noble transition metal colloids to be registered as effective catalysts.Over the past decade, nanoparticles, sometimes also called giant clusters, nanoclusters or colloids have been investigated as nanocatalysts in various catalytic applications such as hydrogenation, C − C coupling and other original reactions. This chapter reviews the recent progress in catalysis with ruthenium and rhodium nanoparticles as soluble nanocatalysts in various liquid media, organized according to the catalytic reaction type. 349Nanoparticles and Catalysis. Edited by Didier Astruc

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Evidence of colloidal rhodium formation during the biphasic hydroformylation of 1-octene with thermoregulated phase-transfer phosphine rhodium(I) catalyst

Cited by 34 publications

References 55 publications

Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

Hydroformylation with Dendritic‐Polymer‐Stabilized Rhodium Colloids as Catalyst Precursors

Rhodium and Ruthenium Nanoparticles in Catalysis

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