Further exploring the “Sting of the Scorpion” : hydride migration and subsequent rearrangement of Norbornadiene to Nortricyclyl on Rhodium(I)

TSOUREAS, Nikolaos, BEVIS, Thomas, BUTTS, Craig P., HAMILTON, Alexander and OWEN, Gareth R. (2009). Further exploring the “Sting of the Scorpion” : hydride migration and subsequent rearrangement of Norbornadiene to Nortricyclyl on Rhodium(I). Organometallics, 28 (17), 5222-5232.

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Official URL: http://dx.doi.org/10.1021/om900499v
Link to published version:: https://doi.org/10.1021/om900499v
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    Abstract

    A new boron-based flexible scorpionate ligand based upon 7-azaindole, Li[Ph(H)B(azaindolyl)2] (Li[PhBai]), has been prepared. This ligand, together with the previously reported ligand K[HB(azaindolyl)3] (K[Tai]), have been used to prepare a range of monovalent group 9 transition-metal complexes. The complexes [M(COD){κ3N,N,H-Ph(H)B(azaindolyl)2}] (where M = rhodium, iridium and COD = 1,5-cyclooctadiene) and [Rh(NBD){κ3N,N,H-HB(R)(azaindolyl)2}] (where NBD = 2,5-norbornadiene and R = Ph, azaindolyl) have been prepared. Structural characterization of [M(COD){κ3NNH-Ph(H)B(azaindolyl)2}] (where M = rhodium, iridium) and [Rh(NBD){κ3N,N,H-HB(azaindolyl)3}] reveal strong interactions of the B−H functional group with the metal centers, particularly in the case of [Ir(COD){κ3N,N,H-Ph(H)B(azaindolyl)2}]. The complex [Rh(NBD){κ3N,N,H-HB(azaindolyl)3}] undergoes a further reaction, resulting from hydride migration from boron to the norbornadiene group. Subsequent rearrangement results in the formation of the rhodium−nortricyclyl complex [Rh(nortricyclyl){κ4N,N,B,N-B(azaindolyl)3}], providing the first nitrogen-based metallaboratrane complex to contain the tetradentate (κ4N,N,B,N) coordination mode.

    Item Type: Article
    Research Institute, Centre or Group - Does NOT include content added after October 2018: Biomolecular Sciences Research Centre
    Identification Number: https://doi.org/10.1021/om900499v
    Page Range: 5222-5232
    Depositing User: Jamie Young
    Date Deposited: 29 May 2015 10:38
    Last Modified: 11 Oct 2018 09:13
    URI: http://shura.shu.ac.uk/id/eprint/9920

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