Selective Hydrogenation of Alkynes Catalyzed by Trinuclear Rhodium Hydride Complexes of the Type [{(Rh[PP*]H)3(μ2‐H)3(μ3‐H)}(BF4)2]

Kohrt, Christina; Wienhöfer, Gerrit; Pribbenow, Cornelia; Beller, Matthias; Heller, Detlef

doi:10.1002/cctc.201300328

Cited by 21 publications

(9 citation statements)

References 29 publications

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“…A very efficient semi‐hydrogenation catalyst is represented by [{(Rh(PP)H) 3 ( μ ‐H) 3 ( μ 3 ‐H)}(BF 4 ) 2 ] (PP=diphosphane). As PP ligands, TangPhos (TangPhos=(1 S ,1′ S ,2 R ,2′ R )‐1,1′‐di‐tert‐butyl‐(2,2′)‐diphopho‐lane) and t Bu‐BisP* ( t Bu‐BisP*=1,2‐bis‐( R , R )‐(tert‐butyl(methyl)‐phosphino)ethane) have been used [4e,17] . In the hydrogenation of the standard test substrate diphenylacetylene (tolane), not only high Z ‐selectivities (up to 98 %) but also a molecular catalyst : substrate ratio of 1 : 10 000 was reached [4e] .…”

Section: Introductionmentioning

confidence: 99%

“…As PP ligands, TangPhos (TangPhos=(1 S ,1′ S ,2 R ,2′ R )‐1,1′‐di‐tert‐butyl‐(2,2′)‐diphopho‐lane) and t Bu‐BisP* ( t Bu‐BisP*=1,2‐bis‐( R , R )‐(tert‐butyl(methyl)‐phosphino)ethane) have been used [4e,17] . In the hydrogenation of the standard test substrate diphenylacetylene (tolane), not only high Z ‐selectivities (up to 98 %) but also a molecular catalyst : substrate ratio of 1 : 10 000 was reached [4e] . However, such multinuclear hydride complexes are expensive and can only be isolated in low yields (15–44 %).…”

Section: Introductionmentioning

confidence: 99%

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Cationic Rhodium Diphosphane Complexes as Efficient Catalysts for the Semi‐Hydrogenation of Dehydroisophytol

Jannsen,

Pribbenow,

Selle

et al. 2023

ChemCatChem

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The selective reduction of terminal alkynes to alkenes was investigated using common cationic diphosphane rhodium complexes of the type [Rh(PP)(diolefin)]X (PP=diphosphane, X=anion). The effectiveness of the catalyst was demonstrated in the semi‐hydrogenation of dehydroisophytol (DIP), an industrial produced intermediate of vitamin E. The present study highlights the high activity and good selectivity of this simple catalytic system. However, deactivation increases at higher DIP concentrations. Several strategies to circumvent the deactivation are presented.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cationic Rhodium Diphosphane Complexes as Efficient Catalysts for the Semi‐Hydrogenation of Dehydroisophytol

Jannsen,

Pribbenow,

Selle

et al. 2023

ChemCatChem

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“…Rh‐based homogeneous catalysts have been widely explored for the semihydrogenation of alkynes since the introduction of Rh complex Wilkinson catalyst in 1965 [8,9] . However, homogeneous systems often suffer from some of the inherent drawbacks, including complicated separation processes and low Rh utilization [10,11] .…”

Section: Introductionmentioning

confidence: 99%

Cu Decorated Rh/TiO₂ Catalyst for Selective Hydrogenation of Phenylacetylene to Styrene

Liu

Zhao

et al. 2021

ChemNanoMat

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Phenylacetylene as an impurity in styrene is poisonous to catalysts for styrene polymerization in the production of polystyrene plastics. The selective hydrogenation of phenylacetylene to styrene is an industrially promising route to overcome this challenge yet lacks cost‐effective catalysts to prevent the overhydrogenation of styrene to ethylbenzene. In this work, we report an efficient and robust copper‐decorated Rh/TiO2 catalyst for the selective hydrogenation of phenylacetylene to styrene. By optimizing the copper coverage on TiO2 supported Rh nanoparticles, we achieved a selectivity of 83% towards styrene formation at a phenylacetylene conversion of 93%. The appropriate Cu coverage is found to modulate the electronic states of surface Rh atoms and changes the Rh exposed active sites, weakening the binding strength of alkene and hydrogen intermediates on Rh and thus mitigating the overhydrogenation and enhancing the selectivity for styrene generation. This work offers insights on the rational design of efficient Rh‐based bimetallic catalysts for selective hydrogenation of phenylacetylene to styrene.

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“…[9] In recent reports similar structure was also found in rhodium-catalyzed hydrogenation. [10] If the NMR spectrum was taken directly after lowtemperature hydrogenation, other species were observed. Two major peaks at d = À17.60 ppm (d, 1 J Ir-H = 41.3 Hz) and at d = À29.78 ppm (br s) were seen in the hydride region of the 1 H NMR spectrum.…”

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confidence: 99%

Mechanism of the Asymmetric Hydrogenation of Exocyclic α,β‐Unsaturated Carbonyl Compounds with an Iridium/BiphPhox Catalyst: NMR and DFT Studies

2014

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The mechanism of the asymmetric hydrogenation of exocyclic α,β-unsaturated carbonyl compounds with the (aS)-Ir/iPr-BiphPhox catalyst was studied by NMR experiments and DFT computational analyses. Computed optical yields of the asymmetric hydrogenation proceeding by an iridium(I)/iridium(III) mechanism involving a transition state stabilized through two intramolecular hydrogen bonds are in good accordance with the experimental ee values.

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Selective Hydrogenation of Alkynes Catalyzed by Trinuclear Rhodium Hydride Complexes of the Type [{(Rh[PP*]H)₃(μ₂‐H)₃(μ₃‐H)}(BF₄)₂]

Cited by 21 publications

References 29 publications

Cationic Rhodium Diphosphane Complexes as Efficient Catalysts for the Semi‐Hydrogenation of Dehydroisophytol

Cationic Rhodium Diphosphane Complexes as Efficient Catalysts for the Semi‐Hydrogenation of Dehydroisophytol

Cu Decorated Rh/TiO₂ Catalyst for Selective Hydrogenation of Phenylacetylene to Styrene

Mechanism of the Asymmetric Hydrogenation of Exocyclic α,β‐Unsaturated Carbonyl Compounds with an Iridium/BiphPhox Catalyst: NMR and DFT Studies

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Selective Hydrogenation of Alkynes Catalyzed by Trinuclear Rhodium Hydride Complexes of the Type [{(Rh[PP*]H)3(μ2‐H)3(μ3‐H)}(BF4)2]

Cited by 21 publications

References 29 publications

Cationic Rhodium Diphosphane Complexes as Efficient Catalysts for the Semi‐Hydrogenation of Dehydroisophytol

Cationic Rhodium Diphosphane Complexes as Efficient Catalysts for the Semi‐Hydrogenation of Dehydroisophytol

Cu Decorated Rh/TiO2 Catalyst for Selective Hydrogenation of Phenylacetylene to Styrene

Mechanism of the Asymmetric Hydrogenation of Exocyclic α,β‐Unsaturated Carbonyl Compounds with an Iridium/BiphPhox Catalyst: NMR and DFT Studies

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Selective Hydrogenation of Alkynes Catalyzed by Trinuclear Rhodium Hydride Complexes of the Type [{(Rh[PP*]H)₃(μ₂‐H)₃(μ₃‐H)}(BF₄)₂]

Cu Decorated Rh/TiO₂ Catalyst for Selective Hydrogenation of Phenylacetylene to Styrene