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Syntheses and X-ray characterization of metal complexes with the pentadentate thiosemicarbazone ligand bis(4-N-methylthiosemicarbazone)-2,6-diacetylpyridine. The first pentacoordinate lead(II) complex with a pentagonal geometry
Authors:Pedrido Rosa  Bermejo Manuel R  Romero M José  Vázquez Miguel  González-Noya Ana M  Maneiro Marcelino  Rodríguez M Jesús  Fernández M Isabel
Institution:Departamento de Química Inorgánica, Facultade de Química, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
Abstract:In this paper we describe the electrochemical synthesis and characterization of new neutral manganese, iron, cobalt, nickel, copper, zinc, cadmium and lead complexes with the ligand bis(4-N-methylthiosemicarbazone)-2,6-diacetylpyridine, H4DAPTsz-Me. X-Ray structures of Mn(H2DAPTsz-Me)(EtOH)2] 1, Pb(H2DAPTsz-Me)] 3 and Zn(H2DAPTsz-Me)]2.EtOH.2H2O 4, were also determined. In these complexes the ligand behaves as bis-deprotonated and SNNNS pentadentate. In the manganese complex the metal is heptacoordinated, in a distorted pentagonal-bipyramidal environment, with the N3S2 donor set of the ligand in the pentagonal girdle and two solvent molecules occupying the axial positions. In the lead complex 3 the metal is pentacoordinated, bound exclusively to the five donor atoms of the ligand, as a consequence of the existence of "inert pair effect". The bishelical zinc complex 4 shows each zinc atom with different coordination geometry, one octahedrally six-coordinate while the other is distorted tetrahedrally four-coordinate.
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