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, Alex 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). pp. 5222-5232. ISSN 0276-7333

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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){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.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
SWORD Depositor: Mx Elements Account
Depositing User: Mx Elements Account
Date Deposited: 01 Nov 2021 11:35
Last Modified: 01 Nov 2021 11:45
URI: http://sro.sussex.ac.uk/id/eprint/102593

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