Bi- and trinuclear oxalamidinate complexes of palladium as catalysts in the copper-free Sonogashira reaction and in the Negishi reaction

The binuclear complex [(acac)Pd(oxam)Pd(acac)] 1 (oxam: tetraphenyl oxalic amidinate) has been prepared from H₂oxam and Pd(acac)₂ in excellent yield. The complex was characterized by elemental analyses, mass spectroscopy, ¹H NMR, ¹³C NMR spectroscopy and in the solid state by X-ray single crystal diffraction analyses. 1 consists of a bimetallic centrosymmetric unit in which the planar oxam ligand acts in a bis-chelating fashion. Each palladium center is in a planar environment.The complex 1 acts as highly selective pre-catalyst in the copper-free Sonogashira reaction between 4-bromoacetophenone and phenylacetylene. Its long-time catalytic activity is higher than that of the related binuclear complex 2 (oxam: tetra-p-tolyl oxalic amidinate) or that of the trinuclear compound [(acac)Pd(oxam)Zn(oxam)Pd(acac)] (3), the solid-state structure of which was also determined by an X-ray structural analysis of single crystals. In addition, 2 is an active and extremely selective pre-catalyst for the Negishi reaction between 3,5,6,8-tetrabromophenanthroline and R-CC-ZnCl (R: Ph, (ⁱprop)₃Si) to form tetra-alkyne-substituted derivatives.