Further exploring the "sting of the scorpion": Hydride migration and subsequent rearrangement of norbornadiene to nortricyclyl on rhodium(i)

Article abstract of DOI:10.1021/om900499v

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){K³N,N,H-Ph(H) B(azaindolyl)₂}] (where M = rhodium, iridium and COD = 1,5-cyclooctadiene) and [Rh(NBD){K³N,N,H-HB(R)(azaindolyl) ₂}] (where NBD = 2,5-norbornadiene and R = Ph, azaindolyl) have been prepared. Structural characterization of [M(COD){K³NNH-Ph(H) B(azaindolyl)₂}] (where M = rhodium, iridium) and [Rh(NBD){k ³N, 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){K³N,N,H-Ph(H)B(azaindolyl)₂}]. The complex [Rh(NBD){K³N,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){k⁴ N,N,-B,N-B(azaindolyl)₃}], providing the first nitrogen-based metallaboratrane complex to contain the tetradentate (K⁴N,N,B,N) coordination mode.