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:: 10.1021/om900499v

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: Biomolecular Sciences Research Centre
Identification Number: 10.1021/om900499v
Depositing User: Jamie Young
Date Deposited: 29 May 2015 10:38
Last Modified: 29 May 2015 10:38
URI: http://shura.shu.ac.uk/id/eprint/9920

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