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Synthesis, properties and structures of complexes of platinum metal halides and Group 11 metals with two distibinomethane ligands, R2SbCH2SbR2 (R = Me or Ph)

Record type: Article

The reaction of [Ru(dmf)(6)][CF3SO3](3), LiX and Ph2SbCH2SbPh2 (dpsm) yielded trans-[RuX2(eta(1)-dpsm)(4)] (X = Cl or Br) or [RuI2(eta(1)-dpsm)(2)(eta(2)-dpsm)]. The latter was shown by an X-ray study to contain two monodentate and one chelating dpsm ligands and is the first example with any metal of a distibinomethane acting as a chelate to be authenticated crystallographically. The chelate ring is highly strained as shown by the Sb-Ru-Sb angle (74.3 degrees) and the longer Ru-Sb distances than in the eta(1)-ligands. Corresponding reactions of trans-[OsX2(dmso)(4)] and dpsm produced trans-[OsCl2(eta(1)-dpsm)(4)] and [OsBr2(eta(1)-dpsm)(2)(eta(2)-dpsm)] identified spectroscopically. The reactions of RhX3 (X = Cl, Br or I) with dpsm afford [RhX3(dpsm)(2)] which on the basis of NMR spectroscopic data contain one chelating and one monodentate dpsm ligand. Palladium(II) and platinum(II) halides form both 1 : 1 and 1 : 2 complexes with dpsm. The former are dimeric and crystal structures of [M2X4(dpsm)(2)] (M = Pt, X = Cl or Br; M = Pd, X = Br) revealed a distibine bridged structure with square-planar MX2Sb2 metal centres, one with a cis geometry, the other trans. The structures cis,trans-[X2M(mu-dpsm)(2)MX2] are the first examples of this geometry to be established crystallographically. In contrast [I2M(mu-dpsm)(2)MI2] are assigned as trans,trans isomers on the basis of spectroscopic data. Multinuclear NMR studies show that [PtX2(dpsm)(2)] (X = Cl or Br) contain eta(1)-dpsm and are a mixture of cis and trans isomers in solution, but the [PtI2(dpsm)(2)] contains only a single form, probably the trans isomer. The [PdX2(dpsm)(2)] have also been characterised and for X = Cl shown to undergo facile fragmentation in solution to form trans,trans-[Pd2Cl2(sigma-Ph)(2)(dpsm)(2)]. The complexes [M(L-L)(2)]Y (M = Cu, Ag or Au; Y = BF4 or PF6; L-L = dpsm or Me2SbCH2SbMe2) and [Rh2Cl2(CO)(2)(mu-L-L)(2)] have also been prepared. All complexes have been characterised by analysis, IR, UV-VIS, multinuclear NMR (H-1, C-13-{H-1}, Pt-195, Cu-63 and Ag-109) spectroscopies as appropriate. Comparisons are drawn between the various co-ordination modes of the distibines and those of Ph2PCH2PPh2 and related ligands.

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Citation

Even, T., Genge, A. R. J., Hill, A. M., Holmes, N. J., Levason, W. and Webster, M. (2000) Synthesis, properties and structures of complexes of platinum metal halides and Group 11 metals with two distibinomethane ligands, R2SbCH2SbR2 (R = Me or Ph) Dalton Transactions, (5), pp. 655-662. (doi:10.1039/a908296d).

More information

Published date: 2000
Keywords: nuclear-magnetic-resonance, crystal-structures, coordination chemistry, homoleptic copper(i), molecular-structures, trans influence, donorligands, bond fission, stibine, triphenylstibine

Identifiers

Local EPrints ID: 18862
URI: http://eprints.soton.ac.uk/id/eprint/18862
ISSN: 1477-9226
PURE UUID: 48ad14fc-9ff7-45f1-b32a-2f514bc7fdeb

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Date deposited: 20 Dec 2005
Last modified: 17 Jul 2017 16:34

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Contributors

Author: T. Even
Author: A. R. J. Genge
Author: A. M. Hill
Author: N. J. Holmes
Author: W. Levason
Author: M. Webster

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