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.

几种新的二铁和铁正森络合物，其中合成了磷化物配体在不同环境中的两个金属单元。发现这些复合物与在轻度条件下的各种炔，二氢丙烷和水地硅烷反应，以使这些小分子被纳入新形成的配体的一部分。辐照得出单和双（生殖）桥梁复合物。当将原发性透射和ETA^5-C_5ME_5复合物得到光化时，还形成了前所未有的双核型复合物，具有两个GE-H-FE 3 Center-2电子键。新的混合配体的系统合成，以及与硫磺的混合金属 - 硫磺属性的混合型金属 - 硫酸化金属核心 - 硫磺的结合剂已获得了固l剂 - 复合物。首次通过在加热上产生了碱基稳定的配合物，从碱基稳定化的基础上生成无基质稳定的配合物，从而首次确认了辅助转换金属 - 甲硅烷基链接（Si = M-Si）上1,3的取代基的迁移。通过在室温下磷酸配体解离16电子IR（I）物种。这种复合物催化了氢二烷烷基分子的分子内重排，从而导致异构化。从同一复合物开始，已经实现了第9组元素的第一个甲硅烷基（Silylene）复合物的合成。

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)。