Discovery and Supramolecular Interactions of Neutral Palladium‐Oxo Clusters Pd₁₆and Pd₂₄

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 [Pd16O24(OH)8((CH3)2As)8] (Pd16) comprises a cyclic palladium‐oxo unit capped by eight dimethylarsinate groups. The chloro‐derivative [Pd16Na2O26(OH)3 Cl3 ((CH3)2 As)8] (Pd16Cl) was also prepared, which forms a highly stable 3D supramolecular lattice via strong intermolecular interactions. The 24‐palladium(II)‐oxo cluster [Pd24O44(OH)8((CH3)2As)16] (Pd24) can be considered as a bicapped derivative of Pd16 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 1H and 13C NMR spectroscopy, 2) in solution by 1H, 13C NMR and 1H DOSY spectroscopic methods, and 3) in the gas phase by electrospray ionization mass spectrometry (ESI‐MS).

Discovery of a Neutral 40-PdII-Oxo Molecular Disk, [Pd40O24(OH)16{(CH3)2AsO2}16]: Synthesis, Structural Characterization, and Catalytic Studies

“…12 ). 19 Metal-oxo clusters can be considered as prenucleated metal nanoclusters which, when distributed uniformly on a support followed by reduction, would lead to metal nanoparticles having controlled sizes that would be largely dependent on the size of the parent metal-oxo cluster. This concept, which was demonstrated recently by utilizing various anionic POPs as model metal-oxo clusters, 14b allows for improved size control of the metal nanoparticles, which is typically difficult to achieve using conventional methods, such as organic ligands, ionic liquids, or dendrimer-stabilized metal nanoparticles.…”

“…This is only the second example of noble metal-oxo clusterbased HOIFs, the first being reported recently by our group. 19 The innate difficulty of controlling the extent of H-bonding interactions between inorganic and organic molecular components is the reason that such types of frameworks are rare. 21 The formation of the 3D HOIF in Pd 40 -SiW 12 is the driving force toward a faster crystallization and a much higher yield (29%) as compared to Pd 40 -Ba (5%).…”

Water‐soluble Self‐assembled {Pd84}Ac Polyoxopalladate Nano‐wheel as a Supramolecular Host

“…First row transition metals are most commonly used, but later transition metals including Pd and Pt have been incorporated [4] . The most recent advances in polyoxopalladate chemistry reveal neutral and cationic cluster families which differ from the majority of polyoxopalladates which are anionic [5–7] . In 2012, the largest polyoxopalladate (POP), {Pd 84 } Ac was reported by Cronin et al.…”