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Chemistry of Transition Metal Supramolecules

过渡金属超分子化学

基本信息

批准号：
07044051
负责人：
OGINO Hiroshi
金额：
$ 2.43万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for international Scientific Research
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07044051/
关键词：
Transition metal Cluster Supramolecule Silicon Germanium Phosphorus Chalcogenide

项目摘要

Several new diiron and iron-ruthenium complexes in which two metal units in different environments are bridged by a phosphido ligand have been synthesized. These complexes were found to react with various alkynes, dihydrosilanes, and hydrodisilanes under mild conditions to give the complexes in which these small molecules were incorporated as parts of newly formed ligands.The primary and secondary germanes were found to react with Cp'Fe (CO)_2SiMe_3 (Cp'=eta^5-C_5H_5, eta^5-C_5Me_5) upon UV irradiation to give mono-and bis (germylene) -bridged complexes. When the primary germane and the eta^5-C_5Me_5 complex were photolyzed, the unprecedented dinuclear complex with two Ge-H-Fe 3 center-2 electron bonds was also formed.New systematic synthesis of mixed-ligand and also mixed-metal transition metal-sulfur trinuclear and tetranuclear clusters has been achieved starting from sulfido-or disulfido-bridged diiron complexes.The facile 1,3-migration of substituents on a silylene-transition metal-silyl linkage (Si=M-Si) was confirmed for the first time by generating base-free silyl (silylene) complexes from base-stabilized ones on heating.The silyltetrakis (phosphine) iridium (I) complex was synthesized for the first time and it was found that this complex generates a 16-electron Ir (I) species by dissociation of a phosphine ligand at room temperature. This complex catalyzes the intramolecular rearrangement of substituents in hydrodisilanes to lead the isomerization. Starting from the same complex, the synthesis of the first silyl (silylene) complex of group 9 element has been achieved.

合成了几种新的二铁和铁钌配合物，其中两个金属单元在不同的环境中被一个膦配体桥接。在温和条件下，这些配合物与各种炔、二氢硅烷和氢化二硅烷反应，生成的配合物中这些小分子作为新形成的配体的一部分，伯、仲锗烷与Cp'Fe（CO）_2SiMe_3反应（Cp '= eta^5-C_5H_5，eta^5-C_5Me_5），得到单、双（锗撑）桥联配合物。当初级锗烷和eta^5-C_5Me_5配合物光解时，也形成了前所未有的具有两个Ge-H-Fe 3中心-2电子键的双核配合物。从硫或二硫桥联的二铁配合物出发，实现了混合配体以及混合过渡金属-硫三核和四核簇合物的新的系统合成。通过生成无碱的甲硅烷基，首次证实了甲硅烯-过渡金属-甲硅烷基键（Si=M-Si）上取代基的3-迁移。（亚甲硅烷基）络合物与碱稳定的络合物在加热时发生反应。首次合成了一种新型的（膦）铱（I）配合物，并发现该配合物在室温下通过膦配体的解离产生16电子的Ir（I）物种。该络合物催化氢化乙硅烷中取代基的分子内重排，导致异构化。从同一配合物出发，合成了第一个9族元素的硅（亚硅基）配合物。