Reusable Catalysts for Hydroformylation‐Based Reactions

Rodrigues, Fábio M. S.; Carrilho, Rui M. B.; Pereira, Mariette M.

doi:10.1002/ejic.202100032

Cited by 29 publications

(13 citation statements)

References 163 publications

(231 reference statements)

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“…Transition metal hydrides are crucial intermediates in a plethora of catalytic reactions, including reactions relevant to (i) energy storage applications, (ii) the synthesis of pharmaceuticals, − and (iii) the preparation of monomers for polymerization . In many of these reactions, hydride transfer (either from a transition metal hydride to a substrate or from a substrate to a transition metal to form a transition metal hydride) is the turnover-limiting step.…”

Section: Introductionmentioning

confidence: 99%

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

et al. 2022

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The kinetics of hydride transfer from Re( R bpy)-(CO) 3 H (bpy = 4,4′-R-2,2′-bipyridine; R = OMe, t Bu, Me, H, Br, COOMe, CF 3 ) to CO 2 and seven different cationic N-heterocycles were determined. Additionally, the thermodynamic hydricities of complexes of the type Re( R bpy)(CO) 3 H were established primarily using computational methods. Linear free-energy relationships (LFERs) derived by correlating thermodynamic and kinetic hydricities indicate that, in general, the rate of hydride transfer increases as the thermodynamic driving force for the reaction increases. Kinetic isotope effects range from inverse for hydride transfer reactions with a small driving force to normal for reactions with a large driving force. Hammett analysis indicates that hydride transfer reactions with greater thermodynamic driving force are less sensitive to changes in the electronic properties of the metal hydride, presumably because there is less buildup of charge in the increasingly early transition state. Bronsted α values were obtained for a range of hydride transfer reactions and along with DFT calculations suggest the reactions are concerted, which enables the use of Marcus theory to analyze hydride transfer reactions involving transition metal hydrides. It is notable, however, that even slight perturbations in the steric properties of the Re hydride or the hydride acceptor result in large deviations in the predicted rate of hydride transfer based on thermodynamic driving forces. This indicates that thermodynamic considerations alone cannot be used to predict the rate of hydride transfer, which has implications for catalyst design.

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Section: Introductionmentioning

confidence: 99%

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

et al. 2022

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“…The attempt started with heterogenization of the soluble catalysts 13 – 16 , which improves the catalyst recyclability but requires complex synthesis procedures for grafting the organic ligands on a solid support. The alternative route is modifying the surface of supported nanoparticle catalysts using excessive phosphine ligands that combined heterogeneous catalyst and organic ligands in the reaction liquor 17 – 19 , but the difficulty in product purification from the solvent containing soluble ligands still limits the wide applications.…”

Section: Introductionmentioning

confidence: 99%

Rhodium nanoparticles supported on silanol-rich zeolites beyond the homogeneous Wilkinson’s catalyst for hydroformylation of olefins

Liu

et al. 2023

Nat Commun

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Hydroformylation is one of the largest industrially homogeneous processes that strongly relies on catalysts with phosphine ligands such as the Wilkinson’s catalyst (triphenylphosphine coordinated Rh). Heterogeneous catalysts for olefin hydroformylation are highly desired but suffer from poor activity compared with homogeneous catalysts. Herein, we demonstrate that rhodium nanoparticles supported on siliceous MFI zeolite with abundant silanol nests are very active for hydroformylation, giving a turnover frequency as high as ~50,000 h−1 that even outperforms the classical Wilkinson’s catalyst. Mechanism study reveals that the siliceous zeolite with silanol nests could efficiently enrich olefin molecules to adjacent rhodium nanoparticles, enhancing the hydroformylation reaction.

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“…Furthermore, phosphites have a rich coordination chemistry, being able to form complexes with most transition metals, particularly with low-valent metal complexes, due to a predominant π-back bonding [ 3 ]. Therefore, they are widely used as outstanding ligands in catalysis [ 3 , 4 ], namely in olefin hydroformylation reactions [ 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. In particular, rhodium(I) complexes modified with bulky aryl monophosphite ligands were found to lead to highly active, chemo- and regioselective catalysts in the hydroformylation of disubstituted and internal double bounds, under relatively mild conditions [ 14 , 15 , 16 ].…”

Section: Introductionmentioning

confidence: 99%

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation

et al. 2022

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Four stereoisomeric monoether derivatives, based on axially chiral (R)- or (S)-BINOL bearing a chiral (+)- or (−)-neomenthyloxy group were synthesised and fully characterised by NMR spectroscopy and X-ray crystallography. The respective tris-monophosphites were thereof prepared and fully characterised. The coordination ability of the new bulky phosphites with Rh(CO)2(acac), was attested by 31P NMR, which presented a doublet in the range of δ = 120 ppm, with a 1J(103Rh-31P) coupling constant of 290 Hz. The new tris-binaphthyl phosphite ligands were further characterised by DFT computational methods, which allowed us to calculate an electronic (CEP) parameter of 2083.2 cm−1 and an extremely large cone angle of 345°, decreasing to 265° upon coordination with a metal atom. Furthermore, the monophosphites were applied as ligands in rhodium-catalysed hydroformylation of styrene, leading to complete conversions in 4 h, 100% chemoselectivity for aldehydes and up to 98% iso-regioselectivity. The Rh(I)/phosphite catalytic system was also highly active and selective in the hydroformylation of disubstituted olefins, including (E)-prop-1-en-1-ylbenzene and prop-1-en-2-ylbenzene.

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Reusable Catalysts for Hydroformylation‐Based Reactions

Cited by 29 publications

References 163 publications

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

Rhodium nanoparticles supported on silanol-rich zeolites beyond the homogeneous Wilkinson’s catalyst for hydroformylation of olefins

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation

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