Synthesis of Tetranuclear Complexes of Pd and Pt with Planar Structures and Development of Their Functionalities

平面结构Pd和Pt四核配合物的合成及其功能开发

基本信息

批准号：
16350028
负责人：
OSAKADA Kohtaro
金额：
$ 9.92万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

This research project aims to synthesize novel tetranuclear platinum and palladium complexes having bridging diarylsilylene ligands and to determine the unique planar structures. Dinuclear Pd and Pt complexes with bridging silylene ligands are obtained with the procedure Which were reported by our group as well as the research group in the States. For example, Pt(PCy_3)_2 functions as a convenient precursor of the dinuclear Pt(I) complexes with two bridging silyl ligands. Heterodinuclear Pd-Pt complex with bridging diphenylsilyl ligand is also obtained from a mixture of Pd(O) and Pt(O) complexes. Reaction of a chelating diphosphine ligand with the dinuclear complexes afforded the Pt_4 complexes and Pt_3Pd complexes. The molecular structures of these complexes have been revealed by X-ray crystallography and by detailed NMR measurement of the solutions. The obtained complexes have four Pt(O) or Pd(O) centers bonded with bridging silylene ligands and metal-metal bonding. Bond lengths and angles show high symmetrical planar structures of the complexes. The DFT calculation for the complexes revealed that the tetranuclear core consists of the zero valent metal centers and neutral silylene ligands. Analogous Pd complexes with bridging diarylgermylene ligands have also been prepared and characterized.The above reaction, forming the tetranuclear complexes, has been followed by the NMR spectroscopy. The reaction is induced by exchange of the monodentate phosphine ligand with the chelating diphosphine ligand. The subsequent condensation of the dinuclear complexes accompanies conversion of the silyl ligand to silylene ligand or germyl ligand to digermene ligand, which leads to formation of the tetranuclear complexes.

该研究项目旨在合成具有桥联二芳基亚甲硅基配体的新型四核铂和钯配合物，并确定其独特的平面结构。采用我们组以及美国研究组报道的程序获得了具有桥连亚硅基配体的双核Pd和Pt配合物。例如，Pt(PCy_3)_2 充当具有两个桥连甲硅烷基配体的双核 Pt(I) 配合物的便利前体。具有桥联二苯基甲硅烷基配体的异双核 Pd-Pt 配合物也可以从 Pd(O) 和 Pt(O) 配合物的混合物中获得。螯合二膦配体与双核配合物的反应提供了Pt_4配合物和Pt_3Pd配合物。这些配合物的分子结构已通过 X 射线晶体学和溶液的详细 NMR 测量揭示。所获得的配合物具有四个与桥连硅基配体和金属-金属键合的 Pt(O) 或 Pd(O) 中心。键长和角度显示配合物的高度对称平面结构。配合物的 DFT 计算表明，四核核心由零价金属中心和中性亚硅基配体组成。还制备并表征了具有桥联二芳基甲锗烷基配体的类似Pd配合物。上述反应形成四核配合物，并通过NMR光谱进行跟踪。该反应是通过单齿膦配体与螯合二膦配体的交换引发的。随后双核络合物的缩合伴随着甲硅烷基配体转化为亚甲硅基配体或甲锗烷基配体转化为二甲烯配体，这导致四核络合物的形成。