title: Synthesis, structure and reactivity of cuboidal-type cluster aqua complexes with W3PdS4 4+ core.
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.
authors.affiliation: Departamento de Química Inorgánica, Universidad de La Laguna, 38200 La Laguna, Tenerife, Spain.
authors.forename: Rita
authors.initials: R
authors.lastname: Hernández Molina
authors.forename: Irina
authors.initials: I
authors.lastname: Kalinina
authors.forename: Maxim
authors.initials: M
authors.lastname: Sokolov
authors.forename: Maria
authors.initials: M
authors.lastname: Clausen
authors.forename: Javier
authors.initials: J
authors.lastname: González Platas
authors.forename: Cristian
authors.initials: C
authors.lastname: Vicent
authors.forename: Rosa
authors.initials: R
authors.lastname: Llusar