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Synthesis and Properties of Transition Metal Complexes Having New Chelate Ligands with Silicon as a Coordinating Atom

以硅为配位原子的新型螯合配体过渡金属配合物的合成及性能

基本信息

批准号：
12640533
负责人：
TOBITA Hiromi
金额：
$ 2.3万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

项目摘要

The purpose of this research was to stabilize silyl ligands and make use of its strong σ-donating ability to activate transition metal complexes. We succeeded in synthesizing a number of transition metal complexes having chelate ligands with silicon as a coordinating atom. In the course of this research, we developed two new methods of preparing complexes having chelate ligands coordinated to the metal through a heteroatom and a silicon :(1) Addition of a polarized double bond to a three-membered metallacycle(2) Addition of an alcohol to a six-membered bis(silylene) complex followed by reductive elimination of an alkoxysilaneIn both methods, the starting complexes themselves had unprecedented structures, so that we carried out the mechanistic studies on the above reactions and the related reactions, and got interesting results.We also synthesized some (2-phosphinoethyl)silylrhodium complexes containing an extremely electron-rich metal center, and found that Rh[(κ^2-Si,P)-Me_2SiCH_2CH_2 … More PPh_2](Pme_3)_2 induces the dehydrocoupling of tert-silane HSiMe_2Ph to give disilane (SiMe_2Ph)_2 in high yield.We prepared the group 8 metal complexes having a bis(silyl) chelate ligand xantsil [(9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)], I.e., (xantsil)M(CO)_4 (M = Fe, Ru, Os), and revealed their X-ray crystal structures containing extremely long metal-silicon bonds. Among them, the ruthenium complex was converted quantitatively to the toluene complex Ru(xantsil)(CO)(η^6-toluene) on simple heating in toluene. The toluene ligand in this complex was found to dissociate readily at room temperature to give a highly coordinatively unsaturated species. Thanks to this unique reactivity, this toluene complex can be led to the complexes having various other ligands under mild conditions, and works as an excellent catalyst for the oligomerization/deoligomerization of HSiMe_2SiMe_3.In conclusion, we found that silyl ligands have a distinctive electronic effect that is stronger than we have expected, and have enough potential to grow as a promising supporting ligand. Less

本研究的目的是稳定硅基配体，并利用其强的σ-贡献能力来活化过渡金属配合物。我们成功地合成了一系列以硅为配位原子的过渡金属螯合物。在这项研究的过程中，我们开发了两种制备具有通过杂原子和硅与金属配位的螯合配体的络合物的新方法：（1）将极性双键加成到三元金属配位化合物上（2）将醇加成到六元双金属配位化合物上在这两种方法中，起始配合物本身具有前所未有的结构，因此我们对上述反应和相关反应进行了机理研究，我们还合成了一些含富电子金属中心的（2-膦乙基）硅基铑配合物，发现Rh[（κ^2-Si，P）-Me_2SiCH_2CH_2 ...更多信息 PPh_2]（Pme_3）_2诱导叔硅烷HSiMe_2Ph的脱氢偶联反应，高产率地得到乙硅烷（SiMe_2Ph）_2。我们合成了具有双（硅基）螯合配体xantsil [（9，9-二甲基氧杂蒽-4，5-二基）双（二甲基硅基）]的8族金属配合物，即，（xantsil）M（CO）_4（M = Fe，Ru，Os）的单晶结构，并揭示了它们含有极长的金属-硅键的X射线晶体结构。其中，钌络合物在甲苯中简单加热时定量转化为甲苯络合物Ru（xantsil）（CO）（η^6-toluene）。发现该配合物中的甲苯配体在室温下容易解离，得到高度配位不饱和物种。由于这种独特的反应活性，这种甲苯配合物可以在温和的条件下与其他各种配体形成配合物，并且可以作为HSiMe_2SiMe_3的齐聚/去齐聚反应的优良催化剂。总之，我们发现硅基配体具有比我们预期的更强的独特的电子效应，并且有足够的潜力作为一种有前途的支持配体。少

项目成果

期刊论文数量（25）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Masaaki Okazaki, Shin Ohshitanai, Masatoshi Iwata, Hiromi Tobita, and Hiroshi Ogino: "Synthesis and Reactivity of (Phosphinoalkyl)silyl Complexes"Coord. Chem. Rev.. 226. 167-168 (2002)

Masaaki Okazaki、Shin Ohshitanai、Masatoshi Iwata、Hiromi Tobita 和 Hiroshi Ogino：“（膦基烷基）甲硅烷基配合物的合成和反应性”坐标。

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通讯作者：

Masaaki Okazaki, Shin Ohshitanai, Hiromi Tobita, and Hiroshi Ogino: "Syntheses, Structure, and Reactivity of {(2-Phosphinoethyl)silyl}rhodium(I) Complexes Rh[(κ^2-Si,P)-Me_2Si(CH_2)_2PPh_2](Pme_3)_n(n=2,3)"J. Chem. Soc., Dalton Trans.. (in press.).

Masaaki Okazaki、Shin Ohshitanai、Hiromi Tobita 和 Hiroshi Ogino：“{(2-膦基乙基)甲硅烷基}铑(I)配合物 Rh[(κ^2-Si,P)-Me_2Si(CH_2) 的合成、结构和反应性” _2PPh_2](Pme_3)_n(n=2,3)"J. Chem. Soc.，Dalton Trans..（正在印刷中）。