Preparation, structure and decomposition of gold(I) and gold(III) acetylide complexes

Oliver Schuster, Ruei Yang Liau, Annette Schier, Hubert Schmidbaur

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43 Scopus citations

Abstract

1-Alkynyl-dimethyl(triorganophosphine)gold(III) complexes of the type cis-Me2(Ph3P)Au-C≡C-R with R = H, Me, Ph (1-3) have been prepared from the cis-Me2(Ph3P)AuX (X = Cl, I) complexes and lithium alkynyls. The crystal structures of 1 and 2 have been determined together with those of the reference compounds cis-Me 2(Ph3P)AuX (X = Cl, I) and cis-Me2(Me 3P)AuI. The molecules have a standard square planar geometry and are not associated into oligomers. Due to the different hybridization of the carbon orbitals, the Au-C(≡CR) bonds are found significantly shorter than the Au-CH3 bonds. Compounds 1-3 are stable colourless, crystalline solids at 20°C but decompose on heating with selective (cis) reductive elimination of ethane and formation of the gold(I) alkynyls (Ph3P)Au-C≡C-R thus retaining the stronger gold-alkynyl bonds. Two complexes of this type have also been prepared by conventional routes from (R3P)AuX complexes and the crystal structures of (Me3P)Au-C≡C-Ph and [(p-Tol) 3P]Au-C≡C-H have been determined. The former with the small Me3P ligand is associated into two different trimers via aurophilic bonding and further aggregated into chains via weak inter-trimer contacts, while the latter is a monomer owing to the steric bulk of the (p-Tol)3P ligand.

Original languageEnglish
Pages (from-to)1429-1441
Number of pages13
JournalInorganica Chimica Acta
Volume358
Issue number5 SPEC. ISS.
DOIs
StatePublished - 15 Mar 2005
Externally publishedYes

Keywords

  • Acetylide ligands
  • Alkynyl ligands
  • Alkynylgold complexes
  • Gold complexes
  • Organogold complexes
  • Reductive elimination

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