A model study of alternative approach toward a class of palladium(II) based self-assembly

Abstract: A different approach developed for the preparation of palladium(II) based complexes [(Pd(bpy)) x (L) y ](NO3)2 x is modelled by using 4-phenylpyridine as ligand (L = 1). Various solvent systems are inspected to optimize the reaction condition for the preparation of the model complex [Pd(bpy)(4-phenylpyridine)2](NO3)2. The model complex is obtained quantitatively as a single product from a 1:1:2 mixture of Pd(NO3)2, 2,2′-bipyridine and 4-phenylpyridine when stirred at room temperature in CH3CN:H2O (1:1). The same reaction is performed in CD3CN:D2O (1:1) to monitor the progress of the reaction by recording 1H NMR. The kinetic products that formed initially got self-healed to give the desired product with in 6h. However, in DMSO-d 6 spontaneous arrangement leading to the targeted complex was observed and no kinetic product could be detected. When a similar reaction is performed with ethylenediamine instead of 2,2′-bipyridine a mixture of compounds are observed. Theoretical calculation throws some light on the principle behind the success of this method for the bpy based systems. The assembly, [Pd(bpy)(4-phenylpyridine)2](NO3)2 has been characterised by NMR, ESI-MS and single-crystal X-ray diffraction methods. [Copyright &y& Elsevier]