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DOI: 10.1039/A701295K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2331-2334

Structural, spectroscopic and redox studies of mer-[RuX3L3] (L = PMe2Ph or AsMe2Ph, X = Cl or Br). Crystal structures of mer-[RuX3(AsMe2Ph)3] (X = Cl or Br) and [Ru2X5(EMe2Ph)4] (X = Br, E = P or As; X = I, E = As)

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Nicholas J. Holmes, Anthony R. J. Genge, William Levason and Michael Webster

Abstract

The complexes mer-[RuX3L3] (X = Cl or Br, L = PMe2Ph or AsMe2Ph) have been re-examined and assignments for their UV/VIS spectra proposed. Attempts to prepare analogues with X = I or L = SbR3 have been unsuccessful. Cyclic voltammetry revealed only irreversible oxidation and reduction processes and chemical oxidation with halogens resulted in decomposition to [RuX6]2-, in contrast to the chemistry of related osmium compounds. The crystal structures of mer-[RuX3(AsMe2Ph)3] (X = Cl or Br) have been determined and confirm the geometrical isomer formed. Crystal structures were also determined for [Ru2X5L4] (X = Br, L = PMe2Ph or AsMe2Ph; X = I, L = AsMe2Ph) obtained by decomposition of mer-[RuX3L3] in solution, which are the first structurally characterised examples of Ru25+ dimers of this type with bromide or iodide co-ligands. The structures are consistent with a formal Ru–Ru bond order of ½.

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