Structures of polynuclear complexes of palladium(ii) and platinum(ii) formed by slow hydrolysis in acidic aqueous solution

Abstract

The aqua ions of palladium(II) and platinum(II) undergo extremely slow hydrolysis in strongly acidic aqueous solution, resulting in polynuclear complexes. The size and structures of these species have been determined by EXAFS and small angle X-ray scattering, SAXS. For palladium(II), the EXAFS data show that the Pd–O and Pd⋯Pd distances are identical to those of crystalline palladium(II) oxide, but the intensities of the Pd⋯Pd distances in the Fourier transform at 3.04 and 3.42 Å are significantly lower compared to those of crystalline PdO. Furthermore, no Pd⋯Pd distances beyond 4 Å are observed. These observations strongly indicate that the polynuclear palladium(II) complexes are oxido- and hydroxido-bridged species with the same core structure as solid palladium(II) oxide. Based on the number of Pd⋯Pd distances, as derived from the EXAFS data, their size can be estimated to be approximately two unit cells, or ca. 1.0 nm³. For platinum(II), EXAFS data of the polynuclear species formed in the slow hydrolysis process show Pt–O and Pt⋯Pt distances identical to those of amorphous platinum(II) oxide, precipitating from the solution studied. The Pt⋯Pt distances are somewhat different from those reported for crystalline platinum(II) oxide. The polynuclear platinum(II) complexes have a similar structure to the palladium ones, but they are somewhat larger, with an estimated diameter of 1.5–3.0 nm. It has not been possible to precipitate any of these species by ultracentrifugation. They are detectable by SAXS, indicating diameters between 0.7 and 2 nm, in excellent agreement with the EXAFS observations. The number of oxido- relative to hydroxido bridges will increase with increasing size of the complex. The charge of the complexes will remain about the same, +4, at growth, with approximate formulas [Pd₁₀O₄(OH)₈(H₂O)₁₂]⁴⁺ and [Pt₁₄O₈(OH)₈(H₂O)₁₂]⁴⁺ for complexes with a size of 2 and 3 unit cells of the corresponding solid metal oxide, respectively. Their high ionic charge in acidic aqueous solution will result in a stabilizing hydration shell.