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Updated: Jul 17, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Synthesis, structure and reactivity of cuboidal-type cluster aqua complexes with W3PdS4 4+ core
Rita Hernández Molina1, Irina Kalinina, Maxim Sokolov
1Departamento de Química Inorgánica, Universidad de La Laguna, 38200 La Laguna, Tenerife, Spain.
Abstract:
The reaction of PdCl(2) with [W3S4(H2O)9]4+ in the presence of hypophosphorous acid in 2 M HCl gives cuboidal cluster [W3(PdCl)S4(H2O)9]3+ (1) which undergoes condensation and crystallises from Hpts solutions as edge-linked double cubane cluster [{W3PdS4(H2O)9}2](pts)(8).19H2O (pts = p-toluenesulfonate) (1'). The substitution of Cl- in (1) by different ligands was explored. The Pd atom in the cluster shows an exceptionally high reactivity in the isomerisation of the hydrophosphoryl H2P(O)(OH), HP(O)(OH)2, HPPh(O)(OH) and HPPh2(O) molecules into the corresponding hydroxo tautomers HP(OH)2, P(OH)3, PhP(OH)2 and Ph2P(OH) stabilised by coordination at Pd. The reactions were followed by UV-Vis spectrophotometry and 31P NMR. Formation constants of the 1 : 1 coordination of [M3(PdCl)S4(H2O)9]3+ (M = Mo, W) with HP(OH)2 and As(OH)3 were obtained. The structures of cucurbit[6]uril (C36H36N24O12, CUC[6]) adducts [W3(PdP(OH)3)S4(H2O)8Cl]-(C36H36N24O12)Cl3.12.5H2O (2), and [W3Pd(PhP(OH)2)S4(H2O)7Cl2]2(C36H36N24O12)Cl4.9H2O (3) were determined by single-crystal X-ray diffraction.
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