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Metathesis Catalyst Removal Techniques

September 30, 2009 By Diana Stoianova

Purification of a metathesis mixture can give you all sorts of problems (especially when using high catalyst loadings). Sometimes you need multiple columns to get a colorless product. Sometimes residual ruthenium can cause the product to isomerize during distillation or decompose over time. Numerous methods have been reported for the removal of metathesis catalysts after a reaction. In general, you need a ligand or adsorbent that binds ruthenium better than your product, or a reagent that will react with the residual ruthenium preferentially. Unfortunately the optimal process tends to vary on a case by case basis.

Published Techniques

  • P(CH2OH)3 (Grubbs, Tetrahedron Lett. 1999, 40, 4137).  The most versatile technique out there. This water-soluble phosphine lets you wash the ruthenium away with an aqueous workup. At least 20 equiv. are necessary for efficient ruthenium removal.
  • P(CH2OH)4Cl + KOH (Pederson, Adv. Synth. Catal. 2002, 344, 728). This generates P(CH2OH)3 from the inexpensive salt.
  • CNCH2CO2K (Diver, Org. Lett. 2007, 9, 1203). This polar isocyanide is much faster than P(CH2OH)3 in quenching the catalyst (~30min) and the complex can be removed by filtration through silica. Unfortunately the isocyanide is not commercially available and takes two steps to prepare.
  • Hydrogenation (Wang, Org. Process Res. Dev. 2008, 12, 226). Hydrogenation with Pd/C following an RCM reaction resulted in removal of residual ruthenium, which is presumably adsorbed onto the solid catalyst.
  • Basic solution of cysteine (Wang, Tetrahedron 2009, 65, 6291). After a RCM in EtOAc, the crude mixture was washed with an aqueous solution of cysteine and NaOH.
  • Activated carbon (Kim, Org. Lett. 2003, 5, 531). Sequential treatments with silica gel, activated carbon, and column chromatography.
  • Amine-functionalized mesoporous silicates (Crudden, Org. Lett. 2006, 8, 2663). This method doesn’t require an aqueous wash or chromatography but a large amount of the adsorbent is used.
  • DMSO or Ph3PO (Georg, Org. Lett. 2001, 3, 1411). Stirring overnight with 50 equiv. followed by column chromatography.
  • Pb(OAc)4 (Paquette, Org. Lett. 2000, 2, 1259). A slight excess (1.5 equiv. per ruthenium) was used followed by silica filtration.
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Comments

  1. Joel says

    November 3, 2009 at 10:04 pm

    Our group has developed a method using 3-mercaptopropionic capped Iron/iron oxide nanoparticles, which may have advantages using magnetic removal.

  2. Joel says

    November 4, 2009 at 12:59 pm

    Err, I guess it would help if I gave the reference. Sorry about that!

    Macdonald, Langmuir, 2008, 24 (14), pp 7169–7177. DOI: 10.1021/la8006734

  3. nickel says

    November 4, 2009 at 3:20 pm

    This has the potential to be a convenient and inexpensive process. Are there other methods out there?

  4. alchemist says

    November 23, 2009 at 1:43 pm

    Wait for an soon to be published Tet. Lett, feature article using hydrogen peroxide! Cheap as chips!

  5. nickel says

    November 30, 2009 at 4:29 pm

    alchemist must have bee talking about the recent David Knight TL paper (Article in Press published Nov. 26, doi: 10.1016/j.tetlet.2009.11.092). They use a simple wash with 15% hydrogen peroxide to kill the catalyst. Worried about over oxidation? The RuO2 that is formed in the process reacts with H2O2 to give H2O and O2, destroying excess peroxide in the process. There are bound to be some functional group incompatibilities, but if it’s as cheap, easy, and effective as it seems, it’s definitely worth a try…

  6. Cp2 says

    April 27, 2010 at 1:12 am

    Hi there,
    i am doing a metathesis rct. with 1st gen. grubbs where the workup is just distilling your product of the reaction mixture leaving you a residue containing a lot of ruthenium (around 15g!! catalyst seperated in three batches). Is there any convienient procedure to recover the ruthenium?
    Thx for help

  7. Diana says

    April 27, 2010 at 6:06 pm

    I assume you want to recover the catalyst and not the ruthenium metal? I doubt that there is much active catalyst left after the reaction and the distillation, most of it is decomposed. But you can try to run a TLC and if there is a spot for the catalyst try to run a column. Good luck!

  8. Cp2 says

    May 3, 2010 at 10:27 pm

    Thx for your answer, but I intended to recover the ruthenium as a metal or as RuCl3 (like in inorganic chemistry lab by dissolution in nitric acid and precipitation as ????…..).
    Maybe there are some people out there how have dealt with “ruthenium waste” and created something useful out of it.

  9. bdfil08 says

    June 9, 2010 at 8:01 am

    Hi all,
    I’m wondering if anyone, except the authors of course, as already had a go at the H2O2 method cited upper (Knghts et al., Tet Lett 2010, 51, 638-640).
    As said, seems really great on the paper.
    What’s the result? Good?
    Anyway, as said also: worth a try so I’ll post my soon-to-be attempt
    Thanks a lot

  10. Simon Byrne says

    October 15, 2010 at 1:45 pm

    I tried the H2O2 method but it didn’t work for me. I’m guessing it oxidised the ruthenium, but also ruined my product.

    The reaction is pretty vigorous too.

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