A series of half-sandwich complexes, [M([9]aneS<SUB>3</SUB>)*XY]<SUP>n</SUP>+ have been synthesised from MCl<SUB>2</SUB> [M = Pd, Pt,X = Y = Cl<SUP>-</SUP>(n = 0), PPh<SUB>3</SUB>0.5dppm, 0.5dppe,0.5x2, 2'-bipy(n = 2), X = Cl<SUP>-</SUP>, Y = PPh<SUB>3</SUB>(n&61 1); M = Pd, X = Y = 0.5oxytriphos, 0.5x1, 10-phen(n = 2), X = Cl<SUP>-</SUP>, Y = PCy<SUB>3</SUB>(n = 1)]. All but one of the crystal structures [M = Pd, X = Y = Cl<SUP>-</SUP>, PPh<SUB>3</SUB>, 0.5dppm, 0.5oxytriphos, 0.5x2,2'-bipy, 0.5x1,10-phen, X = Cl<SUP>-</SUP>, Y&61 PPh<SUB>3</SUB>; M = Pt, X = Y&61 PPh<SUB>3</SUB>, 0.5dppm] solved show the metal in a square-planar, S<SUB>2</SUB>XY co-ordination set, with a long-range apical interaction to the remaining S-atom of [9]aneS<SUB>3</SUB>; [Pt([9]aneS<SUB>3</SUB>)(PPh<SUB>3</SUB>)<SUB>2</SUB>]<SUP>2</SUP>+ is trigonal bipyramidal. The reductive electrochemistry of the Pd complexes shows the stabilisation of Pd(I) species by bidentate, π-acceptor X,Y ligands. A series of complexes [Ru([9]aneS_3)XYZ]^+ (X-Cl^-, Y = CO or PCy_3, Z&61 H or MeCN; X = H, Y = Z = 0.5x1,5-COD) and [Ru([n]aneS_4)*XY]^m+ (X = Cl^-, Y = PPh_3, n = 12,14,16, m&61 1; X = McCN, Y = PPh_3, n = 12,14, m&61 2; X = Y = McCN, n = 16, m = 2) have also been prepared. The crystral structures of [Ru([9]aneS_3)XYZ]^+ (X = Cl^-, Y = CO, Z&61 McCN; X = H, Y = Z = 0.5x1,5-COD) show the metal to be octahedrally co-ordinated. Such is also the case for [Ru([n]aneS_4)XY]^m+ (n = 14,16, X = Cl^-, Y&61 PPh_3; n = 16, X = Y = MeCN), with the non-macrocyclic ligands mutually <i>cis</i>. A study by nmr spectroscopy of the mechanism of formation of [Ru([9]aneS_3)Cl(PPh_3)(C_4H_3O)H^+ ]^- from [Ru([9]aneS_3)Cl_2(PPh_3)] and Et_2O/THF was undertaken. The former complex, and the dimeric intermediates [Ru([9]aneS_3)(PPh_3)Cl]_2^2+ and [Ru([9]aneS_3(PPh_3)(μ2-Cl)Tl(μ3-Cl)]_2^2+ were characterised by X-ray crystallography. Finally, the novel agostic species [Pd(H[9]aneN_3)Cl_2]_2(PF_6)_2.2([Pd(H[9]aneN_3)Cl_2]_2) is described. The X-ray structure of the dimer shows an unsupported Pd-Pd bond with mutally <i>cis</i>-Cl^- ligands. Only one of the two metal ions in the dimer forms an agostic M-H-N bond. The metal in each of the monomers also forms on M-H-N agostic bond. *[9]aneS_3 = 1,4,7-trithiacyclononane, [14]aneS_4 = 1,4,8,11-tetrathiacyclotetradecane [12]aneS_4 = 1,4,7,10-tetrathiacyclododecane, [16]aneS_4 = 1,5,9,13-tetrathiacyclohexadecane.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:661207 |
| Date | January 1991 |
| Creators | Roberts, Yvonne V. |
| Publisher | University of Edinburgh |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/1842/11897 |
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