INOR 194

The reaction of Pb(OOCCH₃)₂·3H₂O with 2.1 equivalents of HS-2,6-(CH₃)₂C₆H₃ in ethanol/water is expected to give Pb(S-2,6-(CH₃)₂C₆H₃)₂. However, we obtained an orange powder whose recrystallisation under nitrogen atmosphere in thf/pentane results in the formation of a mixture of three identifiable crystalline compounds namely [Pb₁₀(S-2,6-(CH₃)₂C₆H₃)₂₀], [Pb₆S(S-2,6-(CH₃)₂C₆H₃)₁₀(C₄H₈O)₄] and [Pb₈O₂(S-2,6-(CH₃)₂C₆H₃)₁₂]. whose crystallization is almost completely separable by controlling its duration and amount of condensed pentane. Recrystallisation of the crude orange powder under aerobic conditions produced pure [Pb₁₄O₆(S-2,6-(CH₃)₂C₆H₃)₁₆] showing its sensitivity to oxidation by oxygen in solution. The structures of the complexes have been characterized via single crystal X-ray analysis along with a characterization of their optical properties. Interestingly, the net formed by the six oxygen and twelve lead atoms in the center of [Pb₁₄O₆(S-2,6-(CH₃)₂C₆H₃)₁₆] resembles a small piece of a layer which forms the solid state structure of red PbO.