|New lead(II) thiolate cluster complexes — Unexpected products of a conventional synthesis |
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.
Dinuclear, Polynuclear and Cluster Chemistry: Frontiers in the New Millennium
7:00 PM-10:00 PM, Sunday, 26 March 2006 Georgia World Congress Center -- Ex. Hall B4, Poster