Triangular Trinuclear Cluster Complexes of Platinum (II)

铂的三角形三核簇配合物 (II)

• 批准号: 08454207
• 负责人: ITO Tasuku
• 金额: $ 5.06万
• 依托单位: Department of Chemistry Graduate School of Science Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454207/
• 关键词: platinum (II) cluster complex; triangular cluster; cluster core transformation; 白金錯体; 白金クラスター

The objective of the present study is synthesis, strucuture, reactivity, and electronic structure of the titled compound whose cluster core structure has been found for the first time by the author's group. Main reults are as follows.1.Establishment of the synthetic method. Desired compounds are derived from tetranuclear platinum (II) cluster complex, [Pt_4 (OAc) _8]. Triangular platinum (II) cluster complexes can be prepared via following two routes, although in-plane ligands are limited to bidentate chelate ligand with nitrogen donors such as glyoxime and diamines.Method A (based on cluster core transformation from the square-planar type). When [Pt_4 (OAc) _8] is allowed to react with glyoximes or diamins in which the surroundings of donor atoms are sterically crowded, desired compounds with the triangular cluster core are prepared through core structure transformation.Method B (based on in-plane ligand substitution of complexes made by Method A). When ethylenediamine or N,N'-dimethy … More lethylendiamine are used as in-plane ligand, Method A is not applicable, but desired compounds are obtained by in-plane ligand substituion of, e.g., glyoxime complexes prepared by Method A.2.Structural studies by means of ^<l95>Pt-, ^<l3>C-, ^1H-NMR and X-ray analyzes. In all the compounds, the cluster core structure was an isosceles triangle. There exist direct Pt-Pt bonds in the cluster core. Magnitude of neclear spin-spin coupling constant J_<Pt-Pt> was 7500-8000 Hz.3.Electronic Structure of the triangular cluster core. EHMO calculation shows that the cluster core of this type is electronically stable, and that platinum atoms at the apices of the triangle are bound by Pt-Pt single bond.4.Substitution lability of the ligand which is in the cluster plane. We had expected labilization by the trans effect of the Pt-Pt bond as in [Pt_4 (OAc) _8] with the square-planar core. Results shows, however, no marked labilization. This is due to the following reasons. All the compounds prepared in this study have nitrogen donor ligands at the in plane sites and Pt-N bond is much stringer than Pt-O bond. Further, glyoxime complexes have intra-molecular hydrogen bonds in the cluster plane. Less

本研究的目的是合成，结构，反应性和电子结构的标题化合物，其簇核结构已被作者的小组首次发现。主要结果如下：1.合成方法的建立。所需化合物来自四核铂（II）簇合物[Pt_4（OAM）_8]。三角形铂（II）簇合物可以通过以下两种途径制备：方法A（基于正方形-平面型簇核的转变），虽然面内配体仅限于具有氮供体的双齿螯合配体，如乙二肟和二胺。方法B（基于方法A制得的配合物的面内配体取代）：将[Pt_4（OAc）_8]与乙二醛或二胺反应，在给体原子周围空间拥挤的情况下，通过核结构的转变，得到具有三角簇核的化合物。当乙二胺或N，N '-二甲基 ...更多信息 乙二胺用作面内配体，方法A不适用，但通过例如，通过方法A.2制备的乙二肟络合物。通过<l95>1H-Pt-、1H-C<l3>-、1H-NMR和X射线分析进行结构研究。所有化合物的簇核结构均为等腰三角形。团簇核心存在直接的Pt-Pt键。核自旋-自旋耦合常数J_（？）<Pt-Pt>为7500-8000 Hz。EHMO计算表明，这种簇核是电子稳定的，三角形顶点的铂原子以Pt-Pt单键结合。4.簇平面内配体的取代不稳定性。我们曾预料到Pt-Pt键的反式作用会使其不稳定，如具有正方形平面核的[Pt_4（OAc）_8]。然而，结果显示没有明显的不稳定性。这是由于以下原因。所有化合物的面内位置都有氮给体配体，Pt-N键比Pt-O键更强。此外，乙二肟络合物在簇平面中具有分子内氢键。少