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Journal of Organometallic Chemistry 689 (2004) 3582–3592 /locate/jorganchem Bi- and trinuclear oxalamidinate complexes of palladium as catalysts in the copper-free Sonogashira reaction and in the Negishi reaction Sven Rau *, Katja Lamm, Helmar Gorls, Julia Schoffel, Dirk Walther ** ¨ ¨ Institut fur Anorganische und Analytische, Chemie der Friedrich-Schiller-Universitat Jena, August-Bebel-Straße 2, 07743 Jena, Germany ¨ ¨ Received 11 May 2004; accepted 2 July 2004 Available online 15 September 2004 Abstract 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 spectr- oscopy 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 ami- dinate) or that of the trinuclear compound [(acac)Pd(oxam)Zn(oxam)Pd(acac)] (3), the solid-state structure of which was also deter- mined by an X-ray structural analys