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接二二元二烯烃配体的新型四核铂和钯络合物，并确定独特的平面结构。用桥接的甲硅琳配体的双核PD和PT复合物通过我们的小组以及各州的研究小组报告的手术获得。例如，pt（pcy_3）_2作为带有两个桥接的甲硅烷基体配体的双核PT（i）配合物的方便前体。还可以从Pd（O）和Pt（O）复合物的混合物中获得杂核PD-PT复合物和桥接二苯基甲硅烷基配体。螯合双氨配体与双核复合物的反应提供了PT_4复合物和PT_3PD复合物。这些复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。所获得的复合物具有与桥接的甲莲烯配体和金属金属键合的四个PT（O）或PD（O）中心。键长和角度显示复合物的高对称平面结构。复合物的DFT计算表明，四核核心由零的瓦伦特金属中心和中性的甲硅琳配体组成。还已经制备并表征了带有桥接二丁二甲苯配体的类似PD复合物。上述反应形成了四核复合物，随后是NMR光谱。反应是通过单次元素磷酸配体与螯合双辣表示配体的诱导的。随后的双核络合物的缩合伴随着甲硅烷基配体向甲硅烷基配体或生殖体配体转化为二甲状腺配体，从而导致形成四核络合物。