New lead(II) thiolate cluster complexes" Unexpected products of a conventional synthesis

INOR 194

Andreas Eichhoefer, eichhoefer@int.fzk.de, Institute of Nanotechnology, Forschungszentrum Karlsruhe, Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
New lead(II) thiolate cluster complexes Unexpected products of a conventional synthesis

The reaction of Pb(OOCCH3)23H2O 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

Sci-Mix
8:00 PM-10:00 PM, Monday, 27 March 2006 Georgia World Congress Center -- Ex. Hall B4, Sci-Mix

Division of Inorganic Chemistry

The 231st ACS National Meeting, Atlanta, GA, March 26-30, 2006