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氧基(羰基)铁或锰配合物的辐照有效地得到了含有金属-硅不饱和键的烷氧基桥联双(硅烯)络合物。X-射线单晶分析揭示了它们独特的结构特征。研究还发现，这些产物的核磁共振信号发生了显著的下场漂移和一些前所未有的反应活性。用不适当的脉冲序列测定了一个双(硅烯)络合物及其相关硅化合物的~&lt；29&gt；Si-^&lt；29&gt；Si耦合常数。耦合常数与EHMO计算得到的3S(Si)-3S(Si)原子轨道布居数成线性关系。我们发现，类似的光反应也可以制备烷氧基桥联的双(锗)和硅烯(锗)络合物。用变温核磁共振研究了这些配合物的动力学行为，揭示了烷氧基…的配位L组对GE的影响比对Si.4弱。我们提出了一种新的一步合成硅烯桥联二铁配合物Cp_2Fe_2(CO)_3(Mu-Sihr)(R=t-Bu，(CME_2)_2H)的新方法，该方法利用了CPFe(CO)_2SiMe_3在RSiH_3存在下的光解反应。此外，在分离中间产物的基础上，我们提出了该反应中CO的光化学解离和氢硅烷的氧化加成和还原消除两次重复的反应机理。我们成功地合成了第一个施主稳定的硅烷三基双核配合物[Cp_2Fe_2(CO)_3(Mu-Sibu^t·给体)]I，并测定了它们的X-射线晶体结构。我们发现，二硅亚铁桥联配合物CPFe(CO)_2-SiMe_2SiMe_2CpFe(CO)_2在辐照后首先转变为硅烯桥联双铁配合物几何异构体的混合物，继而转变为双(硅烯桥联)双铁配合物的几何异构体，并对这些产物进行了X射线晶体结构分析和动力学研究。较少

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。”

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)

Mamoru Shimoi: "Syntheses and crystal structures of [Cr(CO)_5(B_2H_4・2PMe_3)] and [Cr(CO)_4(B_2H_4・2PMe_3)] : the first example of a single hydrogen bridge bond between a metal and a polyborane" Journal of the Chemical Society, Chemical Communication. 199

Mamoru Shimoi：“[Cr(CO)_5(B_2H_4·2PMe_3)]和[Cr(CO)_4(B_2H_4·2PMe_3)]的合成和晶体结构：金属和聚硼烷之间的单氢桥键的第一个例子“化学会杂志，化学通讯。199