Preparation of heterometallic single cubes [W3MS4(H2O)12]n+(M = In, Ge or Sn) and the first corner-shared double cubes [W6SnS8(H2O)18]8+ and [W3Mo3SnS8(H2O)18]8+ as derivatives of [W3S4(H2O)9]4+
Abstract
Conversion of the purple trinuclear WIV3 incomplete cuboidal cluster [W3S4(H2O)9]4+ into heterometallic single cubes of the kind [W3MS4(H2O)12]n+ has been achieved with M = In, Ge or Sn. The indigo blue [W3InS4(H2O)12]5+ product was obtained by reaction of [W3S4(H2O)9]4+ with aquaindium(I), or indium metal, or InIII in the presence of BH4–. Red-brown [W3GeS4(H2O)12]6+ was obtained by reaction with GeO, which can also be regarded as addition of GeII. An alternative route is provided by the reaction with GeO2 and a reducing agent (here H3PO2). Although a crystal structure of [W3(SnCl3)S4(NCS)9]6– has been reported previously, isolation of the yellow-brown aqua ion [W3SnS4(H2O)12]6+ as the chloro product [W3(SnCl3)S4(H2O)9]3+ by addition of SnII to [W3S4(H2O)9]4+ in 2 M HCl is described for the first time. The same product was obtained by treating [W3S4(H2O)9]4+ with tin metal. Charges applying to the core of the cube were determined from the stoichiometry of its reaction with [Fe(H2O)6]3+. In the case of [Mo3S4(H2O)9]4+, reaction with tin metal gave the corner-shared double cube [Mo6SnS8(H2O)18]8+. The W6 analogue was only obtained by the reaction of [W3S4(H2O)9]4+ with [W3SnS4(H2O)12]6+ in the presence of a reducing agent (BH4–). The corresponding reaction of [MoSnS4(H2O)12]6+ gave the mixed corner-shared double cube [W3Mo3SnS8(H2O)18]8+. Near-quantitative transfer of the heterometal atom was observed on treating [W3InS4(H2O)12]5+ or [W3SnS4(H2O)12]6+ with [Mo3S4(H2O)9]4+, indicating a much stronger affinity of the heterometal atom for [Mo3S4(H2O)9]4+.
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