Triangular Trinuclear Cluster Complexes of Platinum (II)

铂的三角形三核簇配合物 (II)

基本信息

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

项目摘要

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

本研究的目的是对本课题组首次发现的簇核结构的化合物进行合成、结构、反应性和电子结构。主要研究结果如下： 1.合成方法的建立。所需化合物衍生自四核铂 (II) 簇络合物 [Pt_4 (OAc) _8]，尽管是在平面内，但可以通过以下两种途径制备。配体仅限于具有氮供体的双齿螯合配体，例如乙二肟和二胺。方法A（基于方形平面类型的簇核转变）当允许[Pt_4(OAc)_8]与乙二肟或二胺反应时，其中。给体原子周围空间拥挤，通过核心结构变换制备具有三角簇核的所需化合物。方法B（基于配合物的面内配体取代当使用乙二胺或N,N'-二甲基乙二胺作为面内配体时，方法A不适用，但可以通过例如制备的乙二肟配合物进行面内配体取代来获得所需的化合物。通过方法A.2。通过^<195>Pt-、^<13>C-、^1H-NMR和X射线嵌入进行结构研究。该化合物的簇核结构为等腰三角形，簇核中存在直接的Pt-Pt键，核自旋-自旋耦合常数J_<Pt-Pt>的大小为7500-8000 Hz。3.电子结构。 EHMO计算表明，该类型的团簇核是电子稳定的，并且三角形顶点的铂原子被Pt-Pt单原子束缚。键。4. 簇平面中配体的取代不稳定性。然而，结果表明，如 [Pt_4 (OAc) _8] 中那样，Pt-Pt 键的反式效应会导致不稳定。，没有明显的不稳定，这是由于本研究中制备的所有化合物在平面位点上都有氮供体配体，并且 Pt-N 键比 Pt-O 键更细。乙二肟配合物在簇平面上具有较少的分子内氢键。