Discovery and Supramolecular Interactions of Neutral Palladium‐Oxo Clusters Pd16 and Pd24. (15th December 2020)

• Record Type: Journal Article
• Authors: Bhattacharya, Saurav; Basu, Uttara; Haouas, Mohamed; Su, Pei; Espenship, Michael Forrester; Wang, Fei; Solé‐Daura, Albert; Taffa, Dereje H.; Wark, Michael; Poblet, Josep M.; Laskin, Julia; Cadot, Emmanuel; Kortz, Ulrich
• Is Part Of: Angewandte Chemie. Volume 133:Number 7(2021)
• Page Start: 3676
• Page End: 3683
• Publication Date: 2020-12-15
• Subjects: inorganic chemistry -- neutral clusters -- organic–inorganic frameworks -- polyoxopalladium -- supramolecular chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202010690
• Languages: English
• ISSNs: 0044-8249

Abstract

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 [Pd16 O24 (OH)8 ((CH3 )2 As)8 ] (Pd16 ) comprises a cyclic palladium‐oxo unit capped by eight dimethylarsinate groups. The chloro‐derivative [Pd16 Na2 O26 (OH)3 Cl3 ((CH3 )2 As)8 ] (Pd16 Cl ) was also prepared, which forms a highly stable 3D supramolecular lattice via strong intermolecular interactions. The 24‐palladium(II)‐oxo cluster [Pd24 O44 (OH)8 ((CH3 )2 As)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 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). Abstract : The first three examples of neutral palladium‐oxo clusters (POCs), Pd16, Pd16 Cl, and Pd24, were prepared by simple open‐pot, room‐temperature reactions of palladium(II) salts in sodium dimethylarsinate aqueous solutions. The dimethylarsinate capping groups act as bidentate, monoanionic ligands for the various palladium‐oxo cores. The three POCs were fully characterized in the solid, solution, and gaseous states by a multitude of physicochemical techniques.