Abstract
The reaction of the bis(thiosemicarbazone) of dimethyl pyridine‐2,6‐diyl diketone, H~2~DAPTSC, with PbMe~2~(OAc)~2~, PbMePh(OAc)~2~ or PbPh~2~(OAc)~2~ in MeOH afforded the complexes [PbMe~2~(DAPTSC)], [PbMePh(DAPTSC)] or [PbPh~2~(DAPTSC)] (in the first two cases together with [Pb(DAPTSC)]). X‐ray crystallography of the Pb(IV) complexes showed that the metal has a pentagonal bipyramidal coordination sphere. The N~3~,S~2~‐bound DAPTSC^2–^ anion occupied the equatorial plane and the organic groups were in the apical positions. These compounds retain the same coordination mode in DMSO solution. DAPTSC^2–^ is also N~3~,S~2~‐bound in [Pb(DAPTSC)], a complex with a stereochemically active Pb^II^ lone pair. The reaction of PbPh~2~Cl~2~ with H~2~DAPTSC, also in methanol at room temperature, afforded [PbPh~2~(H~2~DAPTSC)]~2~[PbPh~2~Cl~4~]Cl~2~·6CH~3~OH. X‐ray crystallography of this centrosymmetric complex showed it to consist of two [PbPh~2~(H~2~DAPTSC)]^2+^ cations of similar structure to the neutral [PbR~2~(DAPTSC)] complexes, together with a trans‐octahedral [PbPh~2~Cl~4~]^2–^ anion and two Cl^–^ anions. This compound decomposes in DMSO solution, probably evolving to H~2~DAPTSC and PbPh~2~Cl~2~(DMSO)~n~. In order to evaluate the changes undergone by H~2~DAPTSC under metallation, the X‐ray structure of the free molecule was also determined.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)