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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，辐照各种烷氧基取代的二硅酰（羰基）铁或锰配合物可以有效地得到含有金属硅不饱和键的烷氧基桥接双（硅）配合物。x射线晶体学揭示了它们独特的结构特征。发现了^<29>Si核磁共振信号的显著下移和这些产物的一些前所未有的反应性。用inept -不充分脉冲序列测定了双（硅炔）配合物和相关硅化合物的^<29>Si-^<29>Si耦合常数。耦合常数与3s (Si) -3s （Si）原子轨道键居数呈线性相关，由EHMO计算得到。我们发现烷氧桥接的双（germylene）和硅烯（germylene）配合物也可以通过类似的光反应制备。利用核磁共振温度依赖性谱对配合物的动力学行为进行了研究，发现烷氧基与Ge的配位比与si的配位弱。利用RSiH_3存在下CpFe(CO)_2SiMe_3的光解作用，提出了一种一步合成硅烯桥接双铁配合物Cp_2Fe_2(CO)_3 (mu-SiHR) （R = t-Bu, (CMe_2)_2H）的新方法。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的光化学解离和氢硅烷的氧化加成和还原消除重复了两次。我们成功合成了第一个供体稳定的硅三基双核配合物[Cp_2Fe_2(CO)_3(mu-SiBu^t·Donor)]，并测定了它们的x射线晶体结构。研究发现，辐照后二苯乙烯桥接的二铁配合物CpFe(CO)_2- sime_2sime_2cpfe (CO)_2首先转变为硅烯桥接的二铁配合物的几何异构体混合物，然后转变为双（硅烯桥接）二铁配合物的几何异构体，CO的连续损失。对这些产物进行了x射线晶体结构分析和动力学研究。少