On solvated tin(iv) ions and the coordination chemistry of high-valent d10 metal ions

Abstract

A very slow oxidation of dimethylsulfoxide (dmso) solvated tin(II) ions in solution results in the formation of a crystalline, structurally determined compound, [CH₃Sn(OS(CH₃)₂)₅](ClO₄)₃, whereas a similar reaction in N,N-dimethylthioformamide (dmtf) forms a crystalline solid with a proposed binuclear [Sn₂(SH)₂(SCHN(CH₃)₂)₈]⁶⁺ entity but whose exact formula remains undetermined. Both solids precipitate with time in their respective mother liquids and constitute the first two tin(IV) and even tetravalent d¹⁰ metal ion solvate complexes ever reported. An EXAFS study showed that the structure of the [CH₃Sn(OS(CH₃)₂)₅]³⁺ complex is identical in solid state and dmso solution. While the exact chemical reaction pathways are unknown, the formation of these complexes constitute a novel way of obtaining solvated tin(IV) ions in standard, commonplace organic media.