Palladium(ii) complexes of N,N-diphenylacetamide based thio/selenoethers and flower shaped PdS and prismatic PdSe nano-particles tailored as catalysts for C-C and C-O coupling.

2-Bromo-N,N-diphenylacetamide (P1) prepared by reacting diphenylamine with α-bromoacetyl bromide, on treatment with NaS and NaSe generated in situ, has resulted in thio and selenoether ligands, L1 ((PhNCOCH)S) and L2 ((PhNCOCH)Se), respectively. Reacting these ligands with NaPdCl in ethanol at room temperature resulted in their complexes [Pd(L1/L2)Cl] (C1/C2). P1, L1, L2, C1 and C2 were characterized by H, C{H} and Se{H} NMR spectroscopy, IR spectroscopy and High resolution mass spectrometry (HR-MS). Single crystal structures of all the five compounds were determined by X-ray diffraction. In both C1 and C2 the geometry of Pd is nearly square planar. Flower shaped PdS (size 26-50 nm) and prismatic PdSe NPs (size 20-55 nm) were synthesized by a single source precursor route (thermolysis at ∼280 °C in trioctylphosphine) from air and moisture insensitive C1 and C2, respectively. These shapes of the two nanophases were unknown hitherto. They were characterized by powder X-ray diffraction (PXRD), SEM-EDX and HR-TEM and found to show good catalytic activity for Suzuki-Miyaura (Pd loading 0.5 mol%; yield up to 96%) and C-O (Pd loading 0.5 mol%; yield up to 96%) coupling reactions (at 100 °C) of aryl bromides with phenylboronic acid and phenol, respectively. The complexes C1 and C2 were found very efficient for Suzuki-Miyaura and C-O coupling as revealed by their optimum loading of 0.0001-0.01 and 0.1 mol% of Pd, respectively, for the two reactions. The reuse of the complexes or NPs as a catalyst is demonstrated.