HOME / PUBLICATIONS /

Publications by Year: 2009

2009
Levason W, Ollivere LP, Reid G, Tsoureas N, Webster M. Synthesis, spectroscopic and structural characterisation of molybdenum, tungsten and manganese carbonyl complexes of tetrathio- and tetraseleno-ether ligands. Journal of Organometallic Chemistry. 2009;694(15):2299 - 2308.Abstract
A range of complexes of the binucleating tetrathio- and tetraseleno-ether ligands, 1,2,4,5-C6H2(CH2EMe)4 (E = S, L3 or Se, L4) or C(CH2EMe)4 (E = S, L5 or Se, L6) and of bidentate analogues 1,2-C6H2(CH2EMe)2 (E = S, L1 or Se = L2) with molybdenum and tungsten carbonyls and manganese carbonyl chloride have been prepared, and characterised by IR and multinuclear NMR (1H, 13C{1H}, 77Se, 55Mn, 95Mo) spectroscopy and mass spectrometry. Crystal structures are reported for [Mo(CO)4(L2)], [Mo(CO)4(L3)], [Mo(CO)4(μ-L3)Mo(CO)4], [Mo(CO)4(L4)], [Mn(CO)3Cl(μ-L3)Mn(CO)3Cl], [Mo(CO)4(μ-L5)Mo(CO)4], [Mn(CO)3Cl(L5)] and two forms (containing meso and DL diastereoisomers) of [W(CO)4(L5)]. © 2009 Elsevier B.V. All rights reserved.
Tsoureas N, Bevis T, Butts CP, Hamilton A, Owen GR. Further exploring the "sting of the scorpion": Hydride migration and subsequent rearrangement of norbornadiene to nortricyclyl on rhodium(i). Organometallics. 2009;28(17):5222 - 5232.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. © 2009 American Chemical Society.
Tsoureas N, Haddow MF, Hamilton A, Owen GR. A new family of metallaboratrane complexes based on 7-azaindole: B-H activation mediated by carbon monoxide. Chemical Communications. 2009;(18):2538 - 2540.Abstract
The reaction of Ir(COD)(Tai) [where Tai = {HB(7-azaindoyl) 3}-] with carbon monoxide results, via a sequence of hydride migration and insertion steps, in the formation of the first complexes to contain a metal-to-boron dative interaction supported by 7-azaindole units. © The Royal Society of Chemistry 2009.