Synthesis, reactivity, and kinetics of substitution in W3PdSe4 cuboidal clusters. A reexamination of the kinetics of substitution of the related W3S4 cluster with thiocyanate.

The reaction of Pd(dba)(2) (dba = dibenzylideneacetone) with [W(3)Se(4)(H(2)O)(9)](4+) in 2 M HCl gives the cuboidal cluster [W(3)(PdCl)Se(4)(H(2)O)(9)](3+), which undergoes edge-to-edge condensation and crystallizes from Hpts solutions as edge-linked double-cubane cluster [{W(3)PdSe(4)(H(2)O)(9)}(2)](pts)(8) x 18 H(2)O (pts(-) = p-toluenesulfonate). The substitution of Cl(-) by different ligands, including phenylsulfinate PhSO(2)(-), was explored. The phenylsulfinate complex was crystallized as a 2:1 adduct with cucurbit[6]uril (C(36)H(36)N(24)O(12)), [W(3)(Pd(PhSO(2))Se(4)(H(2)O)(8.