The Preparation and Selectivity of a Polymer-Attached Rhodium(l) Olefin Hydrogenation Catalyst

Grubbs, Robert H.; Kroll, Leroy C.; Sweet, E. M.

doi:10.1080/10601327308060481

Cited by 111 publications

(26 citation statements)

References 6 publications

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“…Collman et al (25) have found that a similar polymer-attached Rh(1) catalyst, prepared using RhCl(C,H,)-(PPh,), and a PPh,-substituted resin, had similar activity to Wilkinson's catalyst for olefin reduction. In contrast, Grubbs et al found that the anchored Rh(1) catalyst obtained by ligand exchange of RhCl(PPh,), with the same type of resin gave a product which was about 16 times less active per mole of R h (15). We have found no evidence that the specific catalytic activity of either Rh or Ru is enhanced upon anchoring, compared to that of their homogeneous analogs.…”

Section: A Con?parisor~ Of the Catalytic Acticities Of Anchored Specicontrasting

confidence: 44%

The Synthesis and Application of Anchored Catalysts in Hydrogen Isotope Exchange Systems. D₂ – Protic Solvent Exchange

Strathdee¹,

Given²

1974

Can. J. Chem.

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A number of polymer-attached, or anchored, catalysts of rhodium and ruthenium have been synthesized, and their activities for D2 exchange with ethanol have been measured. Among the rhodium anchored catalysts, three exhibited specific activity comparable to Wilkinson's catalyst, RhCl(PPh3)3. No polymer-attached ruthenium species had specific activities close to that of the active homogeneous catalyst RuCl2(PPh3)3. Conditions for the synthesis and optimum loading of complexing resins are discussed. Structural and kinetic comparisons are made between anchored catalysts and their homogeneous analogs.

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Section: A Con?parisor~ Of the Catalytic Acticities Of Anchored Specicontrasting

confidence: 44%

The Synthesis and Application of Anchored Catalysts in Hydrogen Isotope Exchange Systems. D₂ – Protic Solvent Exchange

Strathdee¹,

Given²

1974

Can. J. Chem.

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“…Under these circumstances, a hydrophobic reactant may readily approach the central metal atom via hydrophobic interaction. In contrast, a hydrophilic reactant cannot approach the active site because of the hydrophobic-hydrophilic repulsion in the system [82].…”

Section: Hydrophobic 'Field'mentioning

confidence: 98%

“…On the other hand, with Wilkinson's complex attached to monomeric analogs the difference in rates was quite small. The relevant data are listed in Table III [82). Where a polymeric complex is employed, the active catalytic site is located within a pore in the resin bead.…”

Section: Effect Of Substrate Size and Shape On Selectivitymentioning

confidence: 99%

Polymer-Attached Catalysts

Hirai

Toshima

1986

Catalysis by Metal Complexes

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“…12 The results show a dramatic increase in activity of both the PE catalyst and the PE fiber catalyst over that of the PS bead catalyst (approximately a sixfold increase). While one might argue that porous beads optimized for pore size and surface area would give better results, similar statements may be made for the PE fiber support.…”

Section: Thfmentioning

confidence: 94%

Rhodium (1) catalyst supported on polyethylene hollow fibers: Preparation and hydrogenation studies

Butler¹,

Gordon²,

Harrison³

1988

J of Applied Polymer Sci

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SynopsisIn recent years polymers have been utilized as binding sites for transition metal catalysts (e.g. crosslinked polystyrene beads). However, general problems exist with the above system. The rate of reaction depends on the presence of solvents that adequately swell the polystyrene bead in order to allow access to the catalyst sites. Differences in polarity and reactant size can inhibit diffusion into the bead. Recently a new system has been developed where the catalyst is bound to polyethylene single crystal surfaces, this has solved the above problems. However, polyethylene single crystals are small and plate-like causing a new problem, when trying to filter the separate product the crystals cause clogging of the filtering system and limit the reactions to batch process. This paper describes the use of fine microporous polyethylene hollow fibers as the supporting polymer. This gives the advantages of the single crystal support, plus allows for the use of a fixed-bed flow reaction system. INTRODUCTIONCommercial processes based on homogeneously catalyzed routes are becoming increasingly important. However, these processes can exhibit problems of product contamination and catalyst loss, where products are not readily separated from catalyst. In recent years several attempts have been made to combine the advantages of homogeneous and heterogeneous catalysis.' Anchoring homogeneous catalysts to polymers or other supports effectively " heterogenizes" them, allowing their use in " fixed-bed" type reactions and simplifying catalyst recovery. Thus the problems associated with anchoring homogeneous catalysts has recently been the object of much r e s e a r~h .~,~The most commonly used polymer for supporting catalysts has been crosslinked polystyrene (PS) beads.'-Although PS-supported catalysts show many advantages over homogeneous catalysts, various problems associated with the system have prevented it from being used on an industrial scale. For example, the rate of reaction depends on the presence of solvents that adequately swell the polystyrene beads in order to allow access to the catalytic sites (in the *Author to whom inquiries should be addressed. In the chemical industry large scale processes are typically carried out using a fixed-bed flow reaction process. In this case, reactants can continually flow over a supported catalyst where the reaction takes place. The main advantage of this system over that of the previously mentioned PS or PE-supported catalysts is that a continuous reaction process is maintained. It is not necessary to completely stop the reaction in order to remove the products, instead the product is removed with the flow of the reaction.A new polymer support has been developed that shows potential for use in a fixed-bed flow reaction system. Fine microporous polyethylene hollow fibers (EHF) manufactured by Mitsubishi Rayon Co. have a very high porosity (approx. 60%) and a very small outer diameter (approx. 400 pm).' Wilkinson's catalyst has been bound to these polyethylene hollow fibers. Onc...

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The Preparation and Selectivity of a Polymer-Attached Rhodium(l) Olefin Hydrogenation Catalyst

Cited by 111 publications

References 6 publications

The Synthesis and Application of Anchored Catalysts in Hydrogen Isotope Exchange Systems. D₂ – Protic Solvent Exchange

The Synthesis and Application of Anchored Catalysts in Hydrogen Isotope Exchange Systems. D₂ – Protic Solvent Exchange

Polymer-Attached Catalysts

Rhodium (1) catalyst supported on polyethylene hollow fibers: Preparation and hydrogenation studies

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The Preparation and Selectivity of a Polymer-Attached Rhodium(l) Olefin Hydrogenation Catalyst

Cited by 111 publications

References 6 publications

The Synthesis and Application of Anchored Catalysts in Hydrogen Isotope Exchange Systems. D2 – Protic Solvent Exchange

The Synthesis and Application of Anchored Catalysts in Hydrogen Isotope Exchange Systems. D2 – Protic Solvent Exchange

Polymer-Attached Catalysts

Rhodium (1) catalyst supported on polyethylene hollow fibers: Preparation and hydrogenation studies

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Product

Resources

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The Synthesis and Application of Anchored Catalysts in Hydrogen Isotope Exchange Systems. D₂ – Protic Solvent Exchange

The Synthesis and Application of Anchored Catalysts in Hydrogen Isotope Exchange Systems. D₂ – Protic Solvent Exchange