Chemistry of Transition Metal Supramolecules

过渡金属超分子化学

• 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

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.

已经合成了几种新的二铁和铁钌配合物，其中不同环境中的两个金属单元通过磷配体桥接。发现这些络合物在温和条件下与各种炔烃、二氢硅烷和氢乙硅烷反应，得到其中这些小分子作为新形成的配体的一部分掺入的络合物。发现初级和次级锗烷与 Cp'Fe (CO )_2SiMe_3 (Cp'=eta^5-C_5H_5, eta^5-C_5Me_5) 在紫外线照射下得到单和双（亚甲锗烯） -桥接复合物。当初级锗烷和eta^5-C_5Me_5配合物光解时，还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。混合配体和混合金属过渡金属的新系统合成-硫三核和四核簇已经从硫基或二硫基桥联的二铁配合物开始实现。取代基在a上的​​轻松1,3-迁移通过加热碱稳定的硅基（亚硅基）配合物，首次证实了硅基-过渡金属-硅基键（Si=M-Si）。合成了硅基四（膦）铱（I）配合物首次发现该配合物在室温下通过膦配体的解离产生 16 电子 Ir (I) 物种。该配合物催化氢乙硅烷中取代基的分子内重排，从而导致异构化。从相同的配合物开始，第9族元素的第一个甲硅烷基（亚硅基）配合物的合成已经实现。

项目成果

Amr El-Maradny: "Photoreaction of silyliron (II) complex Cp^*Fe (CO)_2SiMe_3 (Cp^*=η^5-C_5Me_5) in the presence of p-tolygermane" Organometallics. 15. 4954-4958 (1996)

Amr El-Maradny：“硅基铁 (II) 络合物 Cp^*Fe (CO)_2SiMe_3 (Cp^*=η^5-C_5Me_5) 在对甲苯锗烷存在下的光反应”有机金属学 15. 4954-4958 (1996)。

Mikiya Yamada: "Isolation and structural characterization of complexes formed in the reactions of [{C_5H_4 (SiMe_3)}_2Fe_2 (CO)_4] and [{1,3-C_5H_3 (SiMe_3)_2}_2Fe_2 (CO)_4] with elemental sulfur" Bull.Chem.Soc.Jpn.69. 861-867 (1996)

Mikiya Yamada：“[{C_5H_4 (SiMe_3)}_2Fe_2 (CO)_4] 和 [{1,3-C_5H_3 (SiMe_3)_2}_2Fe_2 (CO)_4] 与元素硫反应形成的配合物的分离和结构表征

S. Inomata: "Synthesis and structure of a diiron complex with a highly bent dithiolene bridged, Cp^*_2Fe_2(CO){S_2C_2(CO_2Me)_2}(Cp^*=η-C_5Me_5)" Organometallics. 14. 5490-5492 (1995)

S. Inomata：“具有高度弯曲的二硫烯桥联的二铁配合物的合成和结构，Cp^*_2Fe_2(CO){S_2C_2(CO_2Me)_2}(Cp^*=η-C_5Me_5)”有机金属学。 14. 5490-5492 (1995)

Masaki Okazaki: "Synthesis and structure of the {(2-phosphinoethyl) -silyl} tris (tertiary phosphine) iridium (I) complex Ir {eta^2-Me_2Si (CH_2)_2 PPh_2} (PMe_3)_3" Organometallics. 15. 2790-2793 (1996)

Masaki Okazaki：“{(2-膦乙基)-甲硅烷基}三(叔膦)铱(I)络合物Ir {eta^2-Me_2Si (CH_2)_2 PPh_2} (PMe_3)_3的合成和结构”有机金属。

H. Tobita: "Silylene-bridged dinuclear complexes having a triplet ground state: Photochemical synthesis and structural characterization of Cp_2Fe_2(μ-CO)_2(μ-SiR_2)" Journal of the American Chemical Society. 117. 7013-7014 (1995)

H. Tobita：“具有三重态基态的硅烯桥联双核配合物：Cp_2Fe_2(μ-CO)_2(μ-SiR_2) 的光化学合成和结构表征”美国化学会杂志 117. 7013-7014 (1995)。