Abstract
We report on the synthesis, structure, and physicochemical characterization of the first three examples of neutral palladium-oxo clusters (POCs). The 16-palladium(II)-oxo cluster [Pd(16) O(24) (OH)(8) ((CH(3) )(2) As)(8) ] (Pd(16) ) comprises a cyclic palladium-oxo unit capped by eight dimethylarsinate groups. The chloro-derivative [Pd(16) Na(2) O(26) (OH)(3) Cl(3) ((CH(3) )(2) As)(8) ] (Pd(16) Cl) was also prepared, which forms a highly stable 3D supramolecular lattice via strong intermolecular interactions. The 24-palladium(II)-oxo cluster [Pd(24) O(44) (OH)(8) ((CH(3) )(2) As)(16) ] (Pd(24) ) can be considered as a bicapped derivative of Pd(16) with a tetra-palladium-oxo unit grafted on either side. The three compounds were fully characterized 1) in the solid state by single-crystal and powder XRD, IR, TGA, and solid-state (1) H and (13) C NMR spectroscopy, 2) in solution by (1) H, (13) C NMR and (1) H DOSY spectroscopic methods, and 3) in the gas phase by electrospray ionization mass spectrometry (ESI-MS).