Photo Chemical Syntheses and Reactivities of Organometallic Compounds Containing 4B Elements

含4B元素有机金属化合物的光化学合成及反应活性

• 批准号: 01044013
• 负责人: OGINO Hiroshi
• 金额: $ 2.56万
• 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: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01044013/
• 关键词: photolysis,; silicon-29 NMR,; INEPT-INADEQUATE pulse sequence,; dynamic NMR,; bis (silylene) complex,; bis (germylene) complex,; silylene-bridged complex,; silanetriyl complex

1. We discovered that the irradiation of various alkoxy-substituted disilanyl (carbonyl) iron or manganese complexes efficiently gives alkoxy-bridged bis (silylene) complexes containing metal-silicon unsaturated bonds. Their unique structural features were revealed by X-ray crystallography. The remarkable down field shift of ^<29>Si NMR signals and some unprecedented reactivities of these products were also found.2. The ^<29>Si-^<29>Si coupling constants for a bis (silylene) complex and some related silicon compounds were determined by using the INEPT-INADEQUATE pulse sequence. The coupling constants correlate linearly with 3s (Si) -3s (Si) atomic orbital bond populations which were determined by the EHMO calculation.3. We found that alkoxy-bridged bis (germylene) and silylene (germylene) complexes can also be prepared by the similar photoreaction. Investigation of the dynamic behavior of these complexes by temperature-dependent NMR spectroscopy revealed that the coordination of alkoxy … More l group to Ge is weaker than that to Si.4. We developed a new one-step synthetic method of silylene-bridged diiron complexes Cp_2Fe_2(CO)_3 (mu-SiHR) (R = t-Bu, (CMe_2)_2H) which utilizes the photolysis of CpFe(CO)_2SiMe_3 in the presence of RSiH_3. Furthermore, on the basis of the isolation of the intermediates, we suggested the mechanism of this reaction in which the photochemical dissociation of CO and the oxidative addition and reductive elimination of hydrosilanes are repeated twice.5. We succeeded to synthesize the first donor-stabilized silanetriyl dinuclear complexes [Cp_2Fe_2(CO)_3(mu-SiBu^t・Donor)]I, and determined their X-ray crystal structures.6. We found that upon irradiation a disilanylene-bridged diiron complex CpFe(CO)_2-SiMe_2SiMe_2CpFe(CO)_2 first changes to a mixture of the geometric isomers of silylene-bridged diiron complexes, which then change to the geometric isomers of bis (silylene-bridged) diiron complexes with successive loss of CO's. X-ray crystal structure analyses and kinetic studies were carried out on these products. Less

1.我们发现，各种烷氧基取代的二硅烷基（羰基）铁或锰配合物的辐射有效地得到烷氧基桥接的双（硅亚基）含有金属-硅不饱和键的配合物。X射线晶体学揭示了它们独特的结构特征。实验<29>还发现，这些产物的~ 13 Si NMR信号出现了明显的低场位移，并具有一些前所未有的反应活性.本文<29><29>用INEPT-INADEQUATE脉冲序列测定了一种双硅烯配合物和一些相关硅化合物的^ Si-^ Si偶合常数。耦合常数与EHMO计算确定的3s（Si）-3s（Si）原子轨道键居数线性相关。3.我们发现，烷氧基桥联的双（锗烯）和硅（锗烯）配合物也可以通过类似的光反应制备。通过变温核磁共振谱研究了这些配合物的动力学行为，发现烷氧基的配位 ...更多信息 l基团对Ge的吸附作用弱于对Si的吸附作用。本文提出了一种新的一步合成硅撑桥联二铁配合物Cp_2Fe_2（CO）_3（mu-SiHR）（R = t-Bu，（CMe_2）_2H）的方法，该方法利用CpFe（CO）_2SiMe_3在RSiH_3存在下的光解反应。此外，在分离中间体的基础上，我们提出了该反应的机理，其中CO的光化学解离和含氢硅烷的氧化加成和还原消除重复了两次.成功合成了第一个给体稳定的硅三环配合物[Cp_2Fe_2（CO）_3（mu-SiBu^t·Donor）]I，并测定了其晶体结构.我们发现，二硅撑桥二铁配合物CpFe（CO）_2-SiMe_2SiMe_2CpFe（CO）_2在辐照下首先转变为硅撑桥二铁配合物的几何异构体的混合物，然后转变为双（硅撑桥）二铁配合物的几何异构体，并逐渐失去CO。对产物进行了X射线晶体结构分析和动力学研究。少

项目成果

Keiji Ueno: "Photochemical conversion of a disilanyleneーbridged iron dimer to silyleneーbridged iron dimers" Organometallics. (1991)

Keiji Ueno：“二硅基桥联铁二聚体的光化学转化”有机金属学 (1991)。

Yasuro Kawano: "Synthesis and structure of a donor-stabililzed cationic silanetriyldiiron complex, [Cp_2Fe_2(CO)_3(mu-SiBu^t・NMI)]I(NMI = N-methylimidazole)" Angew. Chem., Int. Ed. Engl.30. (1991)

Yasuro Kawano：“供体稳定的阳离子硅烷三基二铁络合物的合成和结构，[Cp_2Fe_2(CO)_3(mu-SiBu^t·NMI)]I(NMI = N-甲基咪唑)”Angew Chem.，Int。英语30。（1991）

Keiji Ueno: "Evidence for equilibration of 1, 3-alkyl migration in silyl (silylene) iron intermediates." Chemistry Letters. 1990. 369-372 (1990)

Keiji Ueno：“甲硅烷基（亚硅基）铁中间体中 1, 3-烷基迁移平衡的证据。”

Shinji Inomata: "Synthesis, structure, and electrochemical properties of mixed-ligand iron-sulfur cubane clusters with two Cp^* and two dithiolene ligands (Cp^* = eta-C_5H_5, eta-C_5Me_5)." Journal of the American Chemical Society. 112. 6145-6146 (1990)

Shinji Inomata：“具有两个 Cp^* 和两个二硫醇烯配体 (Cp^* = eta-C_5H_5、eta-C_5Me_5) 的混合配体铁硫立方烷簇的合成、结构和电化学性质。”

Yasuro Kawano: "Synthesis and structure of a donorーstabililzed cationic silanetriyldiiron complex,[Cp_2Fe_2(CO)_3(μーSiBu^t・NMI)]I(NMI=Nーmethylimidazole)" Angew.Chem.,Int.Ed.Engl.(1991)

Yasuro Kawano：“供体稳定的阳离子硅烷三基二铁络合物的合成和结构，[Cp_2Fe_2(CO)_3(μ－SiBu^t·NMI)]I(NMI=N－甲基咪唑)” Angew.Chem., Int.Ed.英语(1991)