Sigmatropic Rearrangement on M-E Single and Double Bond System (M = Transition Metal, E = Main Group Element
M-E 单键和双键系统上的 Sigmatropic 重排(M = 过渡金属,E = 主族元素
基本信息
- 批准号:13440193
- 负责人:
- 金额:$ 5.7万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (B)
- 财政年份:2001
- 资助国家:日本
- 起止时间:2001 至 2003
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
In this research project, we have investigated (1) synthesis of transition-metal complexes with unsaturated bonding between metal and main group elements such as silylene and germylene complexes and (2) reactivities of the unsaturated bonding, especially sigmatropic rearrangement between the M-E and M=E bonds (M = transition metal, E = main group element).Silyl(silylene) complexes have been proposed as key intermediates in many transformations of organosilicon compounds mediated by transition metal compounds. However, such complexes are too unstable to isolate due to the electron-deficient nature of the silylene ligand. We have succeeded to stabilize the silyl(silylene) complexes kinetically using bulky Mes substituents (Mes = 2,4,6-C_6H_2Me_3) and isolated the first silyl(silylene)tungsten, molybdenum, and iron complexes. Reaction of the isolated silyl(silylene)iron complex with 'BuNC afforded a disilanyliron complex produced by 1,3-substituent migration from silyl to silylene ligand followed by 1,2-silyl migration from iron to silylene ligand.Photo-irradiation of Cp^*W(CO)_3Me (Cp^* = η-C_5Me_5) in the presence of (2-N,N-dimethylaminophenyl)dimethylsilane gave a silyl complex in which the amino group was coordinated to the tungsten atom. Further irradiation of the silyl complex caused 1,2-aryl migration from silyl to tungsten to form abase-stabilized silylene complex.Irradiation of phosphinosilyliron complex CpFe(CO)_2SiMe_2PPh_2 afforded a novel metallacycle complex with Fe-Si-P three-membered ring. The Fe-Si bond bears unsaturated character due to the contribution of a resonance form with a phosphino-coordinated silylene ligand. Thus reaction of the complex with acetone proceeded via coordination of acetone oxygen to the silylene ligand followed by insertion into the Si-P bond to form a Fe-Si-O-C-P five-membered ring.
本课题主要研究了(1)金属与主族元素之间存在不饱和键的过渡金属配合物的合成,如硅烯配合物和锗烯配合物;(2)不饱和键的反应性,特别是M-E键和M=E键之间的σ迁移重排反应(M =过渡金属,E =主族元素)硅烷基(亚硅烷基)配合物被认为是过渡金属化合物介导的许多有机硅化合物转化反应的关键中间体。然而,由于亚甲硅烷基配体的缺电子性质,这种络合物太不稳定而不能分离。我们成功地用大体积的Mes取代基(Mes = 2,4,6-C_6H_2Me_3)使硅(亚硅基)配合物动力学稳定,并分离出第一批硅(亚硅基)钨、钼和铁配合物。分离的甲硅烷基(亚硅基)铁与BuNC的配合物通过1,3-取代基从硅基向亚硅基配体的迁移和1,2-硅基从铁向亚硅基配体的迁移得到二硅基铁配合物(Cp^* = η-C_5Me_5)(2-N,N-二甲氨基苯基)二甲基硅烷与钨原子配位,得到了氨基与钨原子配位的硅烷基配合物。进一步辐照硅基配合物,使1,2-芳基从硅基向钨基迁移,形成碱基稳定的硅烯配合物,再辐照膦基硅铁配合物CpFe(CO)_2SiMe_2PPh_2,得到一种新型的含Fe-Si-P三元环的金属配合物。Fe-Si键具有不饱和特征,这是由于与膦基配位的亚甲硅烷基配体的共振形式的贡献。因此,配合物与丙酮的反应通过丙酮氧与硅烯配体配位,然后插入Si-P键形成Fe-Si-O-C-P五元环来进行。
项目成果
期刊论文数量(164)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Jim Josephus G.Minglana: "Coordinatively unsaturated Ru(II) species Ru(xantsil)(CO) : A new active catalyst for oligomerization/deoligomerization of HSiMe_2SiMe_3 [xantsi] = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)]. Isolation of a stabilized for
Jim Josephus G.Minglana:“配位不饱和 Ru(II) 物质 Ru(xantsil)(CO):一种用于 HSiMe_2SiMe_3 [xantsi] = (9,9-二甲基呫吨-4,5-二基)双低聚/去低聚的新型活性催化剂
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岡崎雅明: "Synthesis, structure, and reactivity of {(2-phosphinoethyl)silyl}rhodium(I) complexes Rh[(κ^2Si,P)-Me_2Si(CH_2)_2PPh_2](PMe_3)_n(n=2,3)."Organometallics. 21. 2347-2349 (2002)
Masaaki Okazaki:“{(2-膦基乙基)甲硅烷基}铑(I)络合物Rh[(κ^2Si,P)-Me_2Si(CH_2)_2PPh_2](PMe_3)_n(n=2,3)的合成、结构和反应性)。“有机金属学。21。2347-2349(2002)
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M.Okazaki, K.Satoh, T.Akagi, M.Iwata, K.A.Jung, R.Shiozawa, H.Okada, K.Ueno, H.Tobita, H.Ogino: "Convenient Preparation of Li[(η^5-C_5Me_5)M(CO)_2] (M=Ru, Fe) by the Reaction of (η^5-C_5Me_5)M(CO)_2H with n-BuLi"J. Organomet. Chem.. 645. 201-205 (2002)
M.Okazaki、K.Satoh、T.Akagi、M.Iwata、K.A.Jung、R.Shiozawa、H.Okada、K.Ueno、H.Tobita、H.Ogino:“Li的便捷制备[(η^5- (η^5-C_5Me_5)M(CO)_2H 与 n-BuLi 反应的 C_5Me_5)M(CO)_2] (M=Ru, Fe)"J. Organomet. Chem.. 645. 201-205 (2002) )
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結城雅弘: "Cluster construction by reactions of an isomeric pair of trinuclear clusters containing a tetrahiotungstate fragment, [{Cp'Ru(CO)}_2{W(μ-S)_4}] and [{Cp'Ru(CO)}_2{W(=S)(μ3-S)(μ-S)_2}] (Cp' = η^5-C_5Me_5, η^5-C_5Me_4Et), with platinum complexes."Org
Masahiro Yuki:“通过含有四硫钨酸盐片段的同分异构对三核簇的反应构建簇,[{CpRu(CO)}_2{W(μ-S)_4}]和[{CpRu(CO)} _2{W(=S)(μ3-S)(μ-S)_2}] (Cp = η^5-C_5Me_5, η^5-C_5Me_4Et),具有铂络合物。"Org
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飛田博実: "Direct evidence for extremely facile 1,2- and 1,3-group migrations in an FeSi_2 system."Angew.Chem., Int.Ed.. 43. 221-224 (2004)
Hiromi Tobita:“FeSi_2 系统中极其容易的 1,2- 和 1,3-基团迁移的直接证据。”Angew.Chem., Int.Ed.. 43. 221-224 (2004)
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OGINO Hiroshi其他文献
OGINO Hiroshi的其他文献
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{{ truncateString('OGINO Hiroshi', 18)}}的其他基金
Development of teaching m aterials for chemical experiments used in the training course for the renewal of teacher's certificates
教师资格证换发培训班化学实验教材开发
- 批准号:
21500840 - 财政年份:2009
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of teaching materials and kits for chemical experiments in use of remote education
远程教育化学实验教材及套件开发
- 批准号:
19500756 - 财政年份:2007
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of the Route Choice Information System for Elderly and Handicapped Pedestrians
高龄、残障行人选路信息系统的开发
- 批准号:
15560465 - 财政年份:2003
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Synthesis of Stable Silylene and Germylene Complexes and the Mechanistic Studies on Catalytic Reactions Utilizing Them
稳定的亚硅基和亚甲锗烷基配合物的合成及其催化反应机理研究
- 批准号:
09440223 - 财政年份:1997
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Chemistry of Transition Metal Supramolecules
过渡金属超分子化学
- 批准号:
07044051 - 财政年份:1995
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for international Scientific Research
Development of Evaluating System for Elderly Driver Performances using Driving Simulator
利用驾驶模拟器开发老年驾驶员驾驶表现评价系统
- 批准号:
06555159 - 财政年份:1994
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for Developmental Scientific Research (B)
Development of Evaluating System for Elderly Driver Performances using Driving Simulator
利用驾驶模拟器开发老年驾驶员驾驶表现评价系统
- 批准号:
04555133 - 财政年份:1992
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for Developmental Scientific Research (B)
Electronic state of metal complexes and dynamics of their electron transfer reactions
金属配合物的电子态及其电子转移反应的动力学
- 批准号:
03303005 - 财政年份:1991
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for Co-operative Research (A)
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
- 批准号:
01044013 - 财政年份:1989
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for international Scientific Research
An Approach to Metal Cluster Chemistry
金属簇化学的一种方法
- 批准号:
60430011 - 财政年份:1985
- 资助金额:
$ 5.7万 - 项目类别:
Grant-in-Aid for General Scientific Research (A)