Solvents and Ligands Matter: Structurally Variable Palladium and Nickel Clusters Assembled by Tridentate Selenium-...

Structurally variable organochalcogen clusters containing palladium(II) and nickel(II) ions were assembled starting from the salicylidene-substituted dichalcogenides (Y-C₆H₄-N═CH-C₆H₄-OH)₂ ({HL^Y}₂, where Y = Se or Te), and palladium or nickel acetate. The tetrameric palladium clusters contain reduced chalcogenolato ligands {Y-C₆H₄-N═CH-C₆H₄-O)}^2- ({L'^Y}^2-, where Y = Se or Te), while the initially formed trimeric nickel clusters contain the intact, coordinated dichalcogenides. The palladium clusters have a general formula of [Pd₄(L'^Y)₄] and represent the first examples of palladium complexes where both a gyrobifastigial and a pseudocubane arrangement of the central Pd₄Y₄ unit could be established with the same ligand, only depending on the solvents used for crystallization. Reduced density gradient (RDG) considerations based on density functional theory calculations suggest that the commonly referred to stabilizing chalcogen-palladium or palladium-palladium interactions for the two geometric arrangements are weak van der Waals contacts resulting from the contact of two nonbinding lone pairs. In the case of the pseudocubane arrangement, a repulsive steric effect, which is indicated by RDG analysis, is clearly supported by the cuplike distortions detected in the solid-state structure of the compound. In contrast to the reactions with palladium acetate, where the dichalcogenides were cleaved, during similar reactions with nickel acetate, the dichalcogenides remained intact and trimeric clusters of the composition [Ni-μ²-κ²-(Ni{κ⁵-L^Y}₂)₂-μ²-(OAc)₂] (Y = Se, Te) were formed. Air oxidation and hydrolysis of [Ni-μ²-κ²-(Ni{κ⁵-L^Te}₂)₂-μ²-(OAc)₂] gave a rare example of a hexanuclear nickel cluster of the composition [Ni₂-κ⁵-(Ni₄-κ⁶-μ⁶-{(L'^Te₂O₃)(L'^TeO₂)₂}₂)-μ²-(H₂O)₂], which is composed of a well-defined framework consisting of tellurinic anhydride and tellurinate units, which proves the comparably higher oxidation sensitivity of the trinickel dichalcogenide complexes. Electron spray ionization mass spectrometry spectra of both the palladium and nickel clusters indicate that they show fluctional behavior with varying nuclearity in solution and can adopt multiple charge states especially because of the noninnocence of the chalcogen-based ligands. The complexes were fully characterized by spectroscopic methods, elemental analyses, and X-ray diffraction.