权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Reaction Control of Dynamic Complexes with Multiple Bonds of Heavy Group-14 Elements

重14族元素多键动态配合物的反应控制

基本信息

批准号：
14078203
负责人：
KIRA Mitsuo
金额：
$ 31.36万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

During the period of 2002-2004, our study was directed toward the creation of new types of doubly bonded compounds of heavier group-14 element, elucidation of their structure and properties, and control of their unique dynamic properties. The following are the major achievements : As the first compound having formally 5p-hybridized silicon atom, a stable trisilaallene was synthesized using a stable silylene that was synthesized by us in 1999. Related trigermaallene, β-digerrnasilaallene, and β-disilagermaallene were also synthesized. X-ray analysis of these allenes has shown tot in contrast to carbon allenes, all of them have a significantly bent skeleton. As the most remarkable dynamic behavior, trisilaallene and β-disilagermaallene showed temperature dependent dynamic disorder of the central heavy grouo-14 atom. The detailed investigation of the dynamic process both experimentally and theoretically revealed that the process is explained by the facile rotation of the central atom around the terminal two silicon atoms. The dynamic disorder was not observed in the trigermaallene and β-digermasilaallene because of the severe bending at the terminal germanium atoms. Thermally stable silicon-chalcogen doubly bonded compounds (silanethione, silaneseleone, and silanetellone) were synthesized, using our stable dialkylsilylene. The first systematic analysis of the X-ray and UV-vis spectra of a series of silicon-chalcogen doubly bonded compounds revealed the element dependence of the strength of the double bonds and n π^* and n π^* absorption bands. The first 14-electron disilene-palladium complex that was synthesized by the reaction of a bis (phosphine) palladium with a stable disilene was found by the X-ray analysis and theoretical calculations to have the strong jx-disilene complex character.

在2002-2004年期间，我们的研究方向是创建新类型的重14族元素双键化合物，阐明其结构和性质，并控制其独特的动力学性质。主要成果如下：利用我们在1999年合成的稳定的硅烯，合成了第一个具有5位杂化硅原子的化合物--稳定的三硅烯丙二烯。还合成了相关的trigermaallene、β-digernasilaallene和β-disilagermaallene。这些联烯的X射线分析表明，与碳联烯相比，它们都有明显弯曲的骨架。最显著的动力学行为是三硅丙二烯和β-二硅丙二烯，它们的中心重14位原子表现出温度依赖的动力学无序。详细的研究动态过程的实验和理论表明，该过程是由周围的终端两个硅原子的中心原子的轻松旋转解释。由于末端锗原子的严重弯曲，在trigermaallene和β-digermasilaallene中没有观察到动力学无序。利用稳定的二烷基硅烯合成了热稳定的硅硫族双键化合物（硅硫酮、硅烯酮和硅碲酮）。首次系统分析了一系列硅-硫族化合物的X射线和紫外-可见光谱，揭示了双键强度和n π^* 和n π^* 吸收带的元素依赖性。通过X-射线衍射分析和理论计算，发现双膦钯与稳定的二硅烯反应合成的第一个14电子二硅烯钯配合物具有强的二硅烯配合物特征。

项目成果

期刊论文数量（236）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Unusual reactions of isolable dialkylgermylene and dialkylstannylene with galvinoxyl radical

可分离的二烷基亚甲锗烷基和二烷基亚锡亚基与加尔万氧基自由基的异常反应

DOI：
发表时间：
2004
期刊：
Rus.Chem.Bull. 53(5)
影响因子：
0
作者：
Uchio;Y.;Isozaki;Y.;Ota;T.;Utsunomiya;A.;Buslov;M. M.;and Maruyama;S;吉田健太郎;宮岡礼子;H.Masuda
通讯作者：
H.Masuda

Comparison of structures between platinum and palladium complexes of tetrasilyldisilene

四甲硅烷基二硅烯铂与钯配合物的结构比较