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

基本信息

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

项目摘要

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）铁或锰络合物的辐照有效地产生了含有金属-硅不饱和键的烷氧基桥联的双（亚甲硅基）络合物，其独特的结构特征通过X射线晶体学揭示了显着的特征。还发现了 29 Si NMR信号的低场位移以及这些产物的一些前所未有的反应性。2．通过使用INEPT-INADEQUATE脉冲序列测定双(亚甲硅基)络合物和一些相关硅化合物的^ 29 Si-^ 29 Si耦合常数。耦合常数与3s(Si) -3s(Si)线性相关。）通过EHMO计算确定的原子轨道键群。3．通过类似的光反应制备的这些配合物的动态行为通过温度依赖性核磁共振波谱研究表明烷氧基与Ge的配位比与Si的配位弱。4.我们开发了一种新的一步合成方法。亚硅基桥联二铁配合物 Cp_2Fe_2(CO)_3 (mu-SiHR) (R = t-Bu, (CMe_2)_2H) 的光解作用此外，在RSiH_3存在下的CpFe(CO)_2SiMe_3，在分离中间体的基础上，我们提出了该反应的机理，其中CO的光化学解离和氢硅烷的氧化加成和还原消除重复两次。 5. 我们成功合成了第一个供体稳定的硅烷三基双核配合物[Cp_2Fe_2(CO)_3(mu-SiBu^t·Donor)]I，并确定了它们的X射线晶体结构。 6． _2首先转变为亚硅基桥联二铁配合物的几何异构体的混合物，然后转变为以下的几何异构体对这些产物进行了连续损失 CO 的双（亚硅基桥联）二铁配合物。