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Synthesis of metal complexes with highly reactive silicon species as ligands via Si-H bond activation and their reactivity

以高活性硅为配体的Si-H键活化合成金属配合物及其反应活性

基本信息

批准号：
15550045
负责人：
SAKABA Hiroyuki
金额：
$ 1.47万
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：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

1.Studies of synthesis, structure, and reactivity of silylene complexesBase-stabilized hydrido(silylene)tungsten complexes were synthesized via Si-H bond activation of di-and trihydrosilanes, and the following studies were carried out using these complexes. (1)Reaction of cis-Cp^*(CO)_2(H)W=SiHPh・Py (Cp^* = η^5-C_5Me_5) with phenylsilane gave the silyl(silylene) complex trans-Cp^* (CO)_2(PhH_2Si)W=SiHPh・Py, and the formation mechanism was elucidated. (2)Reaction of cis-Cp^*(CO)_2(H)W=SiPhR・L (R = Ph, H ; L = Py, THF) with anionic nucleophiles resulted in the formation of hydrido(silyl) complexes M^+[Cp^*(CO)_2(H)WSiPhRR']^-. Protonation of these anionic complexes gave dihydrido(silyl) complexes Cp^*(CO)_2(H)_2WSiPhRR', whose isomerization and dynamic processes in solution as well as crystal structures were revealed. (3)Hydrido(dichlorosilylene) complex cis-Cp^*(CO)_2(H)W=SiCl_2・Py was synthesized, and interligand hypervalent interaction was observed between the silicon and hydride ligands.2.Studies of synthesis and reactivity of η^3-silaallyl and η^3-silapropargyl complexesNovel η^3-silaallyl complexes Cp^*(CO)_2W(η^3-Me_2SiCR^1CR^2R^3) (R^1-R^3=H, Me) were synthesizes via Si-H bond activation of alkenylhydrosilanes, and their reactivity toward nucleophiles was mainly studied. In the reaction with methanol, silylalkene hydride complexes Cp^*(CO)_2(H)W(η^2-MeOMe_2SiCR^1=CR^2R^3) were formed, and the details of their insertion and isomerization processes were examined. In the Si-H bond activation reaction of alkynylhydrosilanes to synthesize η^3-silapropargyl complex, the unexpected complex Cp^*(CO)_2W(μ-η^1:η^2-C≡C^ΓBu)(SiPh_2) with an alkynyl ligand bridged to the tungsten and silicon atoms was isolated. This unique complex exhibited interesting reactivity toward polar reagents.

1.硅烯基钨配合物的合成、结构及反应性研究通过硅氢键活化二氢硅烷和三氢硅烷，合成了碱稳定的硅烯基钨配合物，并利用这些配合物进行了以下研究。（1）cis-Cp^*（CO）_2（H）W=SiHPh·Py（Cp^* = η^5-C_5Me_5）与苯基硅烷反应，得到了反式-Cp ^*（CO）_2（PhH_2Si）W=SiHPh·Py的硅（亚硅基）配合物，并对其形成机理进行了探讨。（2）cis-Cp^*（CO）_2（H）W=SiPhR·L（R = Ph，H ; L = Py，THF）与阴离子亲核试剂反应，生成了双（硅基）配合物M^+[Cp^*（CO）_2（H）WSiPhRR ']^-。这些阴离子配合物的质子化反应得到了二硅基配合物Cp^*（CO）_2（H）_2WSiPhRR '，并揭示了其在溶液中的异构化和动力学过程以及晶体结构。（3）Hydrido合成了（二氯亚硅基）配合物cis-Cp^*（CO）_2（H）W=SiCl_2·Py，观察到硅和氢配体之间的配体间超价相互作用。2. η^3-硅杂烯丙基和η^3-硅杂炔丙基配合物的合成及其反应性研究新型η^3-硅杂烯丙基配合物Cp^*（CO）_2 W通过硅氢键活化烯基氢化硅烷合成了（η^3-Me_2SiCR^1CR^2R^3）（R^1-R^3=H，Me），并研究了它们与亲核试剂的反应活性。在与甲醇的反应中，生成了硅烯氢化物配合物Cp^*（CO）_2（H）W（η^2-MeOMe_2SiCR^1=CR^2R^3），并详细研究了它们的插入和异构化过程.在炔基氢硅烷的Si-H键活化反应中，合成了η^3-硅炔丙基配合物Cp^*（CO）_2W（μ-η^1：η^2-C C^r Bu）（SiPh_2）。这种独特的配合物对极性试剂表现出有趣的反应性。