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含五齿硫代半卡巴腙配体双(4-N-甲基硫代半卡巴腙)-2,6-二乙酰基吡啶的金属配合物的合成与X射线表征。首例具有五角几何构型的五配位铅(II)配合物。

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.

作者信息

Pedrido Rosa, Bermejo Manuel R, Romero M José, Vázquez Miguel, González-Noya Ana M, Maneiro Marcelino, Rodríguez M Jesús, Fernández M Isabel

机构信息

Departamento de Química Inorgánica, Facultade de Química, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.

出版信息

Dalton Trans. 2005 Feb 7(3):572-9. doi: 10.1039/b416296j. Epub 2004 Dec 20.

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.

摘要

在本文中,我们描述了新型中性锰、铁、钴、镍、铜、锌、镉和铅配合物与配体双(4-N-甲基硫代半卡巴腙)-2,6-二乙酰吡啶(H4DAPTsz-Me)的电化学合成及表征。还测定了[Mn(H2DAPTsz-Me)(EtOH)2] 1、[Pb(H2DAPTsz-Me)] 3和[Zn(H2DAPTsz-Me)]2.EtOH.2H2O 4的X射线结构。在这些配合物中,配体表现为双去质子化的SNNNS五齿配体。在锰配合物中,金属为七配位,处于扭曲的五角双锥环境中,配体的N3S2供体基团位于五角环带,两个溶剂分子占据轴向位置。在铅配合物3中,由于“惰性电子对效应”的存在,金属为五配位,仅与配体的五个供体原子结合。双螺旋锌配合物4显示每个锌原子具有不同的配位几何构型,一个为八面体六配位,另一个为扭曲的四面体四配位。

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