Interaction of organolead(IV) derivatives with formyl- and acetylferrocene thiosemicarbazones: Coordination versus dephenylation or reductive elimination processes |
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| Authors: | J.S. Casas,M.V. Castañ o,M.C. Cifuentes,A. Sá nchez,A. Touceda |
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| Affiliation: | a Departamento de Química Inorgánica, Facultade de Farmacia, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Galicia, Spain
b Departamento de Química Física, Facultade de Farmacia, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Galicia, Spain |
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| Abstract: | The reaction of Ph2PbCl2 with formylferrocene and acetylferrocene thiosemicarbazones (HTSCs) in methanol afforded the corresponding adduct [Ph2PbCl2(HTSC)2] or, in one case, the complex [Ph2PbCl(TSC)]. X-ray crystallography of four of the adducts showed them to be all-trans octahedral complexes with the HTSC ligand S-bound to the metal. The IR spectrum of [Ph2PbCl(TSC)] suggests that the TSC− ligand is N,S-coordinated. The reaction of Ph2Pb(OAc)2 with HTSCs in methanol gave either [Ph2Pb(OAc)2(HTSC)2] or [Ph2Pb(OAc)(TSC)], which was also obtained from Ph3Pb(OAc) via a spontaneous dephenylation process. In the former complexes the HTSC ligand is S-coordinated in the solid state. X-ray crystallography of two of the four [Ph2Pb(OAc)(TSC)] complexes showed that the thiosemicarbazonate anion is N,S-coordinated and the acetate is anisobidentate. Cyclic voltammetry of one [Ph2PbCl2(HTSC)2] adduct and the corresponding [Ph2Pb(OAc)(TSC)] complex showed that the inductive effect of coordination to lead is transmitted to the ferrocenyl group. Surprisingly, the reaction of Me2Pb(OAc)2 with HTSCs afforded only [Pb(TSC)2] complexes, possibly via redistribution and reductive elimination processes. |
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| Keywords: | Diphenyllead(IV) complexes Triphenyllead(IV) Dephenylation Dimethyllead(IV) Reductive elimination Formylferrocene thiosemicarbazones Acetylferrocene thiosemicarbazones X-ray structures Mass spectra IR spectra 1H, 13C and 207Pb NMR spectra Cyclic voltammetry |
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