摘要:
A new boron-based flexible scorpionate ligand based upon 7-azaindole, Li[Ph(H)B(azaindolyl)(2)] (Li[(Ph)Bai]), 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){kappa N-3,N,H-Ph(H)B(azaindolyl)(2)}] (where M = rhodium, iridium and COD = 1,5-cyclooctadiene) and [Rh(NBD){kappa N-3,N,H-HB(R)(azaindolyl)(2)}] (where NBD = 2,5-norbornadiene and R = Ph, azaindolyl) have been prepared. Structural characterization of [M(COD){kappa(3) NNH-Ph(H)B(azaindolyl)(2)}] (where M = rhodium, iridium) and [Rh(NBD){kappa N-3, 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){kappa N-3,NH-Ph(H)B(azaindolyl)(2)}]. The complex [Rh(NBD){kappa(3) NN,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(norticyclyl){kappa N-4,N,B,N-B(azaindolyl)(3)}], providing the first nitrogen-based metallaboratrane complex to contain the tetradentate (kappa N-4,N,B,N) coordination mode.