Synthesis and Photochemistry of Stable Unsaturated Compounds of Group-14 Metals
14族金属稳定不饱和化合物的合成与光化学
基本信息
- 批准号:11440185
- 负责人:
- 金额:$ 9.47万
- 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:1999
- 资助国家:日本
- 起止时间:1999 至 2001
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
The aim of our study has been to synthesize novel stable group-14 element unsaturated compounds and to reveal their structure and reactions.The following are the major results: (1) Unusual reactions of stable dialkylsilylene with dichloromethane and chloromethylcyclopropane were discovered. The results were explained by invoking the ambiphilic nature of silylene. (2) The reactions of the electronically excited silylene with benzene derivatives were first observed. The excited silylene should have the nature of the singlet 1,1-biradical. (3) An apparent discrepancy for the dimer structure of bis(diisopropyl-amino)silylene between experiment and theory was solved by the detailed theoretical study. (4) Rates and mechanism of the E,Z-isomerization in tetrakis(trialkylsilyl)disilenes were revealed. (5) Unique mechanisms of the reactions of disilenes with alcohols and chloroalkanes were proposed on the basis of the theoretical and experimental studies. (6) A new silyllithium reagent, a 1,2-d … More ilithiodisilane (1), was prepared by the reaction of a tetrakis(trialkylsilyl)disilene with lithium in THF. (7) A 1,3-disilabicyclo[1.1.0]butane was synthesized using the reaction of the 1,2-dilithio-disilane 1 with a ketone. The disilabicyclobutane was found to have a unique inverted σ bridge bond. (8) A disilene-platinum complex, which has a metallacyclopropane type structure, was synthesized using the reaction of 1 with a dichloroplatinum and its structure was determined by X-ray crystallography. (9) A silicon-bowtie compound (spiropentasiladiene), whose carbon analogs have never been isolated, was first synthesized. The unique spiro-conjugation in the molecule was revealed by X-ray crystallography and theoretical calculations. (10) A stable 4-silatriafulvene having an Si=C bond with inverted polarity was synthesized and characterized by X-ray crystallography and various spectroscopies.All these results will contribute to construct a new concepts of structure and bonding in the chemistry of main-group elements and to offer the basic structures for the future functional materials. Less
本论文旨在合成新型稳定的十四族元素不饱和化合物,并揭示其结构和反应,主要结果如下:(1)发现了稳定的二烷基硅烯与二氯甲烷和氯甲基环丙烷的不寻常反应。结果被解释为调用的两亲性的性质的硅烯。(2)首次观察到电子激发的硅烯与苯衍生物的反应。激发的亚硅基应具有单线态1,1-双自由基的性质。(3)通过详细的理论研究,解决了双(二异丙基氨基)硅烯的二聚体结构与实验值之间的明显差异。(4)揭示了四(三烷基硅基)二硅烯的E,Z-异构化速率和机理。(5)在理论和实验研究的基础上,提出了二硅烯与醇和氯代烷烃反应的独特机理。(6)一种新的硅基锂试剂,1,2-d ...更多信息 通过四(三烷基甲硅烷基)二硅烯与锂在THF中的反应制备硫代二硅烷(1)。(7)利用1,2-二硫代二硅烷1与酮的反应合成1,3-二硅双环[1.1.0]丁烷。发现二硅双环丁烷具有独特的倒σ桥键。(8)利用1与二氯铂的反应合成了一种具有金属环丙烷型结构的二硅烯铂配合物,并用X射线单晶衍射法测定了其结构。(9)首次合成了一种硅蝴蝶结化合物(spiropentasiladiene),其碳类似物从未被分离出来。通过X射线晶体学和理论计算揭示了分子中独特的螺共轭结构。(10)合成了一种稳定的具有Si=C键且极性相反的4-硅三富烯,并通过X射线晶体学和各种光谱学手段对其进行了表征,这些结果将有助于在主族元素化学中建立一个新的结构和成键概念,并为未来功能材料提供基础结构。少
项目成果
期刊论文数量(271)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
A.F.Stange: "Ruthenium and rhenium complexes with silyl-substituted bipyridyl ligands"J.Organomet.Chem.. 612. 117-124 (2000)
A.F.Stange:“具有甲硅烷基取代的联吡啶配体的钌和铼络合物”J.Organomet.Chem.. 612. 117-124 (2000)
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T.Manaka: "Large order-disorder transition in polydihexylsilane films as studied by second-harmonic generation spectroscopy"Chem. Phys. Lett.. 317. 260-263 (2000)
T.Manaka:“通过二次谐波产生光谱研究聚二己基硅烷薄膜中的大有序-无序转变”Chem。
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- 影响因子:0
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M.Takahashi: "Theoretical study on stereochemical diversity in the addition of water to disilene"Organometallics. 19(23). 4660-4662 (2000)
M.Takahashi:“二硅烯加水立体化学多样性的理论研究”有机金属学。
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- 影响因子:0
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吉良満夫: "有機量子化学「ケイ素など高周期14族元素化合物の電子構造と反応」"朝倉書店. 24 (2001)
吉良光男:“有机量子化学‘硅等高周期14族元素化合物的电子结构和反应’”朝仓书店。24(2001)
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- 影响因子:0
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W. Setaka, C. Kabuto, and M. Kira: "An ESR study of a tetrasilaspirobiindane anion radical. Stereoelectronic electron-accepting effects of a trialkylsilyl group"Chem. Lett.. (4). 317-318 (1999)
W. Setaka、C. Kabuto 和 M. Kira:“四硅螺二茚满阴离子自由基的 ESR 研究。三烷基甲硅烷基的立体电子电子接受效应”Chem。
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KIRA Mitsuo其他文献
KIRA Mitsuo的其他文献
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{{ truncateString('KIRA Mitsuo', 18)}}的其他基金
Theoretical Approach to Structural Issues of Heavy Main-Group Element Compounds
重主族元素化合物结构问题的理论方法
- 批准号:
22550028 - 财政年份:2010
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
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
- 批准号:
14078203 - 财政年份:2002
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas
Creation, Structure, and Reactivity of Novel Hypercoordinate Organosilicon Compounds
新型超配位有机硅化合物的创造、结构和反应性
- 批准号:
05640587 - 财政年份:1993
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for General Scientific Research (C)
Synthesis, Structure, and Functions of Low-Valent Organosilicon, -germanium, and -tin Compounds
低价有机硅、锗、锡化合物的合成、结构和功能
- 批准号:
02640375 - 财政年份:1990
- 资助金额:
$ 9.47万 - 项目类别:
Grant-in-Aid for General Scientific Research (C)