Catalysts For Hydroformylation Of Olefins Research Articles

Rational solvent selection for the preparation of industrial monolithic supported liquid-phase (SLP) olefin hydroformylation catalyst

Heterogenisation of the hydroformylation (HyFo) process converting C4 olefins and syngas (CO/H2) to n-pentanal can substantially reduce its carbon footprint by simplifying downstream processing. Current upscaling efforts include constructing a pilot plant containing a Rh-diphosphite-stabilized supported liquid-phase (SLP) catalyst. The air-sensitive nature of the catalyst requires in-situ impregnation of the porous support material with the liquid phase components (Rh-precursor, ligand, stabiliser) entailing the use of large quantities of an organic solvent. Environment, health, and safety (EHS) as well as regulatory aspects prompt the search for an alternative to dichloromethane (DCM), which was used as standard solvent for lab-scale studies. To obtain alternatives to DCM, the replacement solvent methyl tert-butyl ether (MTBE) and in-silico screening of more than 5000 solvent candidates has been performed covering boiling points and solubility predictions by COSMO-RS as well as carcinogenicity- and mutagenicity predictions by quantitative structure–activity relationship (QSAR) models. The final list of solvent candidates contained unsaturated compounds (alkenes, alkynes) in addition to ether- and ester-functionalized​ solvents, which are typically recommended as DCM replacements. Sufficiently high solubilities of ligand and stabiliser to prepare the desired SLP catalyst were experimentally determined in the following solvents: methyl propionate (MP), dimethoxymethane (DMM), MTBE, tetrahydrofuran (THF) and DCM for benchmarking, and a monolithic SLP catalyst prepared with MTBE demonstrated to perform equally well in the HyFo reaction of 1-butene as the benchmark catalyst prepared using DCM solvent. Overall, the study demonstrates a practical approach for selecting solvents with a greener profile for making catalyst systems applicable for large-scale production.

Containing Nitrogen and Phosphorus Porous Organic Polymer-Supported Rhodium Catalyst for Hydroformylation of Olefins

Containing Nitrogen and Phosphorus Porous Organic Polymer-Supported Rhodium Catalyst for Hydroformylation of Olefins

Outlook of Cobalt-Based Catalysts for Heterogeneous Hydroformylation of Olefins: From Nanostructures to Single Atoms

Outlook of Cobalt-Based Catalysts for Heterogeneous Hydroformylation of Olefins: From Nanostructures to Single Atoms

Nitrogen‐containing Porous Organic Polymer Supported Rhodium Catalyst for Hydroformylation of Olefins

AbstractThe hydroformylation reaction of olefins with syngas (CO/H2) to manufacture aldehydes is one of the largest homogeneous catalytic processes. However, it is important to extend the use of Rh catalysts promoted by nitrogen ligands to heterogeneous system. In this study, a nitrogen‐containing porous organic polymer supported Rh catalyst (Rh/TImT‐TBPT) was successfully synthesized, as well as showed excellent catalytic activity (TOF=216 h−1) and selectivity of aldehydes (98 %) in the hydroformylation of 1‐octene. Furthermore, the catalytic performance of Rh/TImT‐TBPT in the hydroformylation of various olefins was also investigated, displaying outstanding results. The catalytic material was characterized by FT‐IR, XRD, XPS, TEM, SEM and TGA in detail. The characterization data showed that Rh species were highly dispersed on the support, leading to the good stability. More importantly, the Rh/TImT‐TBPT catalyst could be separated from the reaction system at the end of the hydroformylation, and then reused in the next cycle under optimized conditions.

Fabrication of the Microenvironment and Active Structure of Single-Rh-Site Catalysts for Efficient Hydroformylation of Olefins

Fabrication of the Microenvironment and Active Structure of Single-Rh-Site Catalysts for Efficient Hydroformylation of Olefins

Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins

Single-atom Rh catalysts present superior activity relative to homogeneous catalyst in olefins hydroformylation, yet with limited success in regioselectivity control. In the present work, we develop a phosphorus coordinated Rh1 single-atom catalyst with nanodiamond as support. Benefiting from this unique structure, the catalyst exhibits excellent activity and regioselectivity in hydroformylation of arylethylenes with wide substrate generality, i.e., with high conversion (>99%) and high regioselectivity (>90%), which is comparable with the homogeneous counterparts. The coordination interaction between Rh1 and surface phosphorus species is clarified by 31P solid-state NMR and X-ray absorption spectroscopy (XAS). Rh single atoms are firmly anchored over nanodiamond through Rh-P bonds, guaranteeing good stability in the hydroformation of styrene even after six runs. Finally, by using this catalyst, two kinds of pharmaceutical molecules, Ibuprofen and Fendiline, are synthesized efficiently with high yields, demonstrating a new prospect of single-atom catalyst in pharmaceutical synthesis.

Exploration of Stable and Phosphine Ligand Free Heterogeneous Catalyst for Ethylene Hydroformylation

The development of highly active,stable and phosphine ligand free heterogeneous catalyst for hydroformylation reaction remains an open challenge.Herein,we developed highly active,stable and phosphine ligand free heterogeneous catalyst for ethylene hydroformylation reaction by replacing single strongly coordinating phosphine ligand with multiple weakly coordinating oxygen functional groups on the activated carbon surface.Applying of the typical Rh/C-3 catalyst in hydroformylation of ethylene affords unprecedented turnover frequencies(TOFs)up to 57889/h.Besides,the Rh/C-3 catalyst exhibited substantially improved stability in the hydroformylation of ethylene in a fixed-bed reactor(at least 2500 h).For the first time,detailed characterizations revealed that lactone group(-CO2-)on the surface of activated carbon might play a crucial role to gain this catalyst with remarkable activity and stability,which facilitate the homogeneous dispersion and stability of Rh nanoparticles.This work provides a general guidance for the design of highly active,stable and phosphine ligand free heterogeneous catalysts for hydroformylation of olefins.

Organic Ligand‐Free Hydroformylation with Rh Particles as Catalyst†

Summary of main observation and conclusionAn efficient and organic ligand‐free heterogeneous catalytic system for hydroformylation of olefins is highly desirable for both academy and industry. In this study, simple Rh black was employed as a heterogeneous catalyst for hydroformylation of olefins in the absence of organic ligand. The Rh black catalyst showed good catalytic activity for a broad substrate scope including the aliphatic and aromatic olefins, affording the desired aldehydes in good yields. Taking the hydroformylation of ethylene as an example, 86% yield of propanal and TOF of 200 h–1 were obtained, which was superior to the reported homogeneous catalytic systems. In addition, the catalyst could be reused five times without loss of activity under identical reaction conditions, and the Rh leaching was negligible after each cycle.

Porous Organic Polymer Supported Rhodium as a Reusable Heterogeneous Catalyst for Hydroformylation of Olefins.

A new porous organic polymer has been prepared via copolymerization of divinyl-functionalized phosphoramidite ligand and tris(4-vinylphenyl)phosphine. The porous polymer was loaded with Rh(acac)CO2 to yield a supported Rh catalyst, which demonstrated good regioselectivity ( l/ b = 6.7-52.8) and high catalytic activity (TON up to 45.3 × 104) in hydroformylation of terminal and internal olefins. Remarkably, the heterogeneous catalyst can be reused at least 10 cycles without losing activity and selectivity in hydroformylation of 1-hexene.

A dinuclear phosphite rhodium(I) complex obtained by syngas treatment of a Rh/hydroxy phosphonite olefin hydroformylation precatalyst.

A hydroxy phosphonite was found to be unstable during the catalyst preformation routine applied towards a rhodium olefin hydroformylation catalyst. C-P bond cleavage occurred when the phosphonite was reacted with [(acac)Rh(1,5-COD)] (acac is acetyl acetate and 1,5-COD is cycloocta-1,5-diene) at 80 °C and 20 bar of CO/H2. As a result, a nearly planar six-membered ring structure consisting of two rhodium(I) cations and two bridging phosphorous acid diester anions was formed, namely bis[μ-(4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]-1:2κ2P:O;1:2κ2O:P-bis{[6-([1,1'-biphenyl]-2-yloxy)-4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphepine-κP]carbonylrhodium(I)} toluene tetrasolvate, [Rh2(C22H28O5P)2(C34H37O5P)2(CO)2]·4C7H8. Further coordination of phosphite and of carbonyl groups resulted in 16-electron rhodium centres.

Dual Rh-Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols.

An active and selective dual catalytic system to promote domino hydroformylation-reduction reactions is described. Apart from terminal, di- and trisubstituted olefins, for the first time the less active internal C-C double bond of tetrasubstituted alkenes can also be utilized. As an example, 2,3-dimethylbut-2-ene is converted into the corresponding n-alcohol with high yield (90 %) as well as regio- and chemoselectivity (>97 %). Key for this development is the use of a combination of Rh complexes with bulky monophosphite ligands and the Ru-based Shvo's complex. A variety of aromatic and aliphatic alkenes can be directly used to obtain mainly linear alcohols.

ChemInform Abstract: The Rhodium Complex of Bis(diphenylphosphinomethyl)dopamine‐coated Magnetic Nanoparticles as an Efficient and Reusable Catalyst for Hydroformylation of Olefins.

AbstractA new bis(diphenylphosphinomethyl)dopamine (bpd) ligand is prepared and anchored on the surface of magnetic nanoparticles (MNP).

The rhodium complex of bis(diphenylphosphinomethyl)dopamine-coated magnetic nanoparticles as an efficient and reusable catalyst for hydroformylation of olefins

MNPs functionalized with new bis(diphenylphosphinomethyl)dopamine (bpd) for hydroformylation reaction.

Poly(ethylene glycol)-stabilized Rh nanoparticles as efficient and recyclable catalysts for hydroformylation of olefins

Abstract Poly(ethylene glycol) (PEG)-stabilized Rh nanoparticles prepared by simple hydrogen reduction of RhCl 3 ·3H 2 O in the presence of PEG 4000 (PEG with an average molecular weight of 4000 g/mol) were shown to be efficient and recyclable catalysts for hydroformylation of olefins in thermoregulated PEG biphasic system, which allows for not only an efficient homogeneous catalytic reaction, but also an easy biphasic separation and reuse of catalyst. Under the optimized conditions, the conversion of various olefins and the yield of corresponding aldehydes were ≥ 98%. The Rh nanoparticle catalyst could be separated from products by simple phase separation and recycled for twenty times without evident loss of activity.

Rh Nanoparticles Catalyzed Hydroformylation of Olefins in a Thermoregulated Ionic Liquid/Organic Biphasic System

Rh nanoparticles were investigated as a catalyst for hydroformylation of olefins in thermoregulated ionic liquid/organic biphasic systems composed of an ionic liquid, namely [CH 3 (OCH 2 CH 2 ) 16 N + Et 3 ][CH 3 SO 3 − ] (IL PEG750 ), and an organic solvent. This enables not only a homogeneous reaction but also easy biphasic separation. Under the optimized reaction conditions, the conversion of 1-octene and yield of aldehyde were 99% and 91%, respectively. The catalyst was easily separated from the product by phase separation and used eight times without evident loss of activity. 将具有“高温混溶、室温分相”功能的离子液体[CH 3 (OCH 2 CH 2 ) 16 N + Et 3 ][CH 3 SO 3 – ] (IL PEG750 ) 与甲苯-正庚烷组成的两相体系用于纳米 Rh 催化的烯烃氢甲酰化反应中, 在优化的反应条件下, 1-辛烯转化率和醛收率分别为 99% 和 91%. 催化剂经简单分相即可与产物分离, 且可连续使用 8 次, 其活性基本保持不变. Rh nanoparticles were used as a catalyst for hydroformylation of olefins in thermoregulated ionic liquid/organic biphasic system, giving a homogeneous reaction and biphasic separation.

Rhodium(I) N-Heterocyclic Carbene Complexes as Catalysts for Hydroformylation of Olefins: An Overview

The present state of art on the application of carbene-rhodium complexes as stable catalysts for hydroformylation reaction is described. A critical analysis of the influence of pressure and temperature on the hydroformylation of non-modified rhodium complexes and those ones described in the presence of carbenes is also done. Finally, a set of experiments using NHCs prepared by us at different reactions conditions is presented and discussed. Keywords: Aliphatic olefins, hydroformylation, rhodium, N-heterocyclic carbene ligands, Rhodium-NHC Complexes, Rhodium-Carbonyl Complexes, Influence of pressure, styrene, Influence of Temperature

Coprecipitated Gold–Tricobalt Tetraoxide Catalyst for Heterogeneous Hydroformylation of Olefins

Abstract The combination of gold (Au0) and tricobalt tetraoxide (Co3O4) prepared by coprecipitation gives high-performance heterogeneous catalysts for hydroformylation reaction with selectivity above 85% in desired aldehydes, although neither Au0 nor Co3O4 have been demonstrated in this reaction and show poor activities. The Au/Co3O4 catalysts can be recycled by simple decantation with slight decrease in catalytic activity along with recycle times. The role of Au may mainly promote in situ reduction of Co3O4 to Co0 catalyzing the hydroformylation reaction.

Organometallic Supramolecular Mixed-Valence Cobalt(I)/Cobalt(II) Aquo Complexes Stabilized with the Water-Soluble Phosphine Ligandp-TPPTP (p-triphenylphosphine triphosphonic acid)

Reaction of the water-soluble phosphine phosphonic acid p-TPPTP(H)6 (p-triphenylphosphine triphosphonic acid) with Co2(CO)8 under biphasic conditions results in the formation of Co6(CO)3(p-TPPTP)2(H2O)24·24H2O (2) or Co4(CO)3(p-TPPTP)2(H2O)24·24H2O (3) depending on the pH of the solution. These supramolecular organometallic Co(I)/Co(II) complexes contain either six (2) or four (3) crystallographically distinct cobalt ions. The cation [Co(CO)3(p-TPPTP)2]+ from 2 was reacted with titanium tetraisopropoxide via a sol−gel method to give a titania-supported Co(I) olefin hydroformylation catalyst, which was characterized using solid-state 31P NMR, IR, and XPS.

Rhodium-calix[6]arene diphosphite complex as olefin hydroformylation catalyst

A rhodium-calix[6]arene diphosphite complex was used as a catalyst in the hydroformylation reaction of linear alkenes and styrenes. The influence of P/Rh and substrate/catalyst ratios, as well as temperature and pressure, on the aldehyde yield and the regioselectivity of the process was studied. The complexation of calix[6]arene diphosphite with Rh(acac)(CO)2 was studied by 1H and 31P NMR spectroscopy and atmosphericpressure electrospray ionization (AP-ESI) mass spectrometry.

Preparation and performance of anchored heterogenized rhodium complex catalyst for hydroformylation

In order to solve the difficult problem in separation of homogeneous catalyst from the reaction mixture, heterogenized rhodium carbonyl complex catalyst for hydroformylation of olefins was prepared by copolymerization of functionalized 3-aminopropyltriethoxysalane with tetraethoxysalane (TEOS) via the sol–gel method. The catalyst was characterized by FT-IR, X-ray photoelectron spectroscopy (XPS), ICP and N 2 absorption. The activity, selectivity and stability of this catalyst for 1-hexene hydroformylation have been examined. It was concluded the activity depended on the surface area of the catalyst matrix, which varied according to the pH in the sol–gel process. The conversion of 1-hexene reached 98.8%, with a selectivity of 99.6% of aldehydes and the n/ i ratio of 0.86 under optimized conditions. Furthermore, it showed excellent stability and reusability, the catalyst was used for six times without obvious loss of activity.