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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Synthesis, Crystal Structures, and Properties of S-Bridged Pt(II)-Ni(II) Dinuclear Complexes: conversion of Square-Planar [Ni(aet)_2] to Octahedral Geometry by Forming an S-Bridged Structure with Pt(II) (aet=2-Aminoethanethiolate)
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Synthesis, Crystal Structures, and Properties of S-Bridged Pt(II)-Ni(II) Dinuclear Complexes: conversion of Square-Planar [Ni(aet)_2] to Octahedral Geometry by Forming an S-Bridged Structure with Pt(II) (aet=2-Aminoethanethiolate)

机译：S桥Pt（II）-Ni（II）双核配合物的合成，晶体结构和性质：通过与Pt（II）形成S桥结构，将方形平面[Ni（aet）_2]转变为八面体几何（aet = 2-氨基乙硫醇盐）

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摘要

The reactions of [Ni(aet)_2] with [PtCl_2(L)] gave a new type of S-bridged dinuclear complexes [Pt(L){Ni(aet)_2(H_2O)_2}]~(2+) (aet=aminoethanethiolate; L=bpy=2,2'-bipyridine, phen=1,10-phenanthroline (5), dmbpy=4,4'-dimethyl-2,2'-bipyridine). These complexes readily react with L' to form [M(L){Ni(aet)_2(L')}]~(2+) (L=bpy, L'=bpy (3), phen; L=phen, L'=phen, bpy; L=L'=dmbpy). A similar reaction of [Ni(aet)_2] with [PtCl_2(phen)] and phen gave only [Pt(phen){Ni(aet)_2(phen)}]~(2+). The crystal structures of 3 and 5 were determined by X-ray crystallography. The Ni atoms are surrounded by two aet and a bpy or two water molecules to have an approximately octahedral geometry, forming the C_2-cis(S)-[Ni(aet)_2{bpy or (H_2O)_2}] unit. The Pt atoms have a square-planar geometry, in which two Cl atoms of the starting [PtCl_2(L)] (L=bpy or phen) have been substituted by the two S atoms from the Ni(II) unit. The Pt(II) plane and the Ni(II) equatorial plane are almost coplanar, and the Pt-Ni distance is 3.4987(8) A (3) and 3,476(4) A (5). All of the complexes were characterized on the basis of the electronic absorption and infrared spectra and the cyclic voltammetry. The conversion of a square-planar [Ni(aet)_2] to an octahedral [Ni(aet)_2{(H_2O)_2 or (L')}] units was also considered. In the solid state, the water molecule in [Pt(L){Ni(aet)_2(H_2O)_2}]~(2+) could be readily exchanged by nitrate.
机译：[Ni（aet）_2]与[PtCl_2（L）]的反应产生了一种新型的S桥连双核络合物[Pt（L）{Ni（aet）_2（H_2O）_2}]〜（2+）（ aet ＝氨基乙硫醇盐; L ＝ bpy ＝ 2，2′-联吡啶，phen ＝ 1，10-菲咯啉（5），dmbpy ＝ 4，4′-二甲基-2，2′-联吡啶）。这些络合物容易与L'反应形成[M（L）{Ni（aet）_2（L'）}]〜（2+）（L = bpy，L'= bpy（3），phen; L = phen， L'= phen，bpy; L = L'= dmbpy）。 [Ni（aet）_2]与[PtCl_2（phen）]和phen的相似反应仅产生[Pt（phen）{Ni（aet）_2（phen）}]〜（2+）。通过X射线晶体学测定3和5的晶体结构。 Ni原子被两个aet和bpy或两个水分子包围，以具有近似八面体的几何形状，形成C_2-顺式（S）-[Ni（aet）_2 {bpy或（H_2O）_2}]单元。 Pt原子具有正方形平面的几何形状，其中起始[PtCl_2（L）]的两个Cl原子（L = bpy或phen）已被来自Ni（II）单元的两个S原子取代。 Pt（II）平面和Ni（II）赤道平面几乎共面，Pt-Ni距离为3.4987（8）A（3）和3,476（4）A（5）。根据电子吸收和红外光谱以及循环伏安法对所有配合物进行表征。还考虑了将方形[Ni（aet）_2]转换为八面体[Ni（aet）_2 {（H_2O）_2或（L'）}]单位的转换。在固态下，[Pt（L）{Ni（aet）_2（H_2O）_2}]〜（2+）中的水分子很容易被硝酸盐交换。

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