Pentahapto-bonded gold heteroborane clusters [3-(R3P)-closo-2,1-AuTeB10H10]- and [3-(R3P)-closo-3,1,2-AuAs2B9H9]-.

Gold acetylide compounds [(R3P)AuC[triple bond]CC(Me)(OH)Et], where R = Ph 1 or cyclohexyl (Cy) 2, were synthesised and 2 was characterised using X-ray diffraction techniques. The solid-state structure of 2 contained a two-coordinate gold atom and a linear P-Au-C[triple bond]C-C bonding sequence. The reactions between 1 or 2 and [NR4][nido-7,8-As2B9H10] or [NR4][nido-7-TeB10H10] in ethanol-acetone solvent afforded the twelve-vertex cluster species [NMe4][3-(R3P)-closo-3,1,2-AuAs2B9H9], where R = Ph 5 or Cy 6, or [NEt4][3-(R3P)-closo-2,1-AuTeB10H10], where R = Ph 7 or Cy 8, in moderate or low yields (ca. 35% for , and and ca. 20% for ). Compounds and were characterised with X-ray crystallographic techniques. Although there was crystallographic disorder in the {As2B3} and {TeB4} rings to which the gold atoms were attached, the structures of 5 and 7 strongly suggested that the gold atoms were pentahapto bonded to all the atoms in the {As2B3} or {TeB4} rings giving formally closo cluster geometries with closo cluster electron counts. The solution-phase NMR properties of 5, 6 and 7 were consistent with closo descriptions.