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REACTION FIELD CREATED BY METAL COMPLEXES

金属络合物产生的反应场

基本信息

批准号：
07305039
负责人：
SUZUKI Hiroharu
金额：
$ 3.52万
依托单位：
TOKYO INSTITUTE OF TECHNOLOGY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

This research project was intended to establish the methodology for the construction and modification of the reaction field of metal complex. The reaction field created on the metal complex can be modified by appropriately changing ligands. Ten researchers working in a variety of fields have been divided into the following four groups.1. Creation of Highly Functioned Mononuclear Active SpeciesTakashi ito, Kohtaro Osakada, and Sanshiro Komiya2. Construction of Sterically and Electronically Controlled Multimetallic Reaction FieldHiroharu Suzuki, Kiyashi Isobe, and Kazuyuki Tatsumi3. Conversion of Organic Substrates in the Highly Controlled Metal Complex Reaction FieldTamotu Takahashi and Yasuo Wakatsuki4.Theoretical Approach directed toward Control of Reaction FieldNobuaki Koga and Shigeyoshi SakakiThe first group achieved activation of CO_2, Si-C bond, and N-H bond by using coordinatively unsaturated transition metal complexes. The second group developed systematic synthetic method of metal cluster complexes. Di- and trinuclear polyhydride complexes of ruthenium could activate a variety of organic substrates including alkanes and unprecedented type of selective C-H and C-C bonds cleavage was performed. A new class of clusters with Rh-S-W framework were systematically synthesized. A novel organic transformation involving zirconacyclopentene as synthetic intermediate and redox reaction of NO on hexanuclear carbonyl clusters were performed by the third group. Ab initio MO studies of several transition metal complex-catalyzed reactions such as olefin polymerization and hydrosilation were done by the fourth group.

本研究旨在为金属络合物反应场的构建和修饰奠定方法学基础。在金属络合物上产生的反应场可以通过适当改变配体来改变。在不同领域工作的十名研究人员被分成以下四组。创造高功能的单核活性物种伊藤隆太郎、大阪田幸太郎和小宫三郎2。空间和电子控制的多金属反应场的构建铃木广春、清水等边和和之达美3。有机底物在高度可控的金属络合物反应领域的转化高桥康夫和若津康夫4.控制反应场的理论方法古贺信明和佐木重吉利用配位的不饱和过渡金属络合物实现了CO_2、Si-C键和N-H键的活化。第二组发展了金属簇合物的系统合成方法。Ru的双核和三核聚氢化物配合物可以激活包括烷烃在内的多种有机底物，并进行了前所未有的选择性C-H键和C-C键的断裂。系统地合成了一类具有Rh-S-W骨架的新型簇合物。第三组进行了以锆环戊烯为合成中间体的新型有机转化和NO在六核羰基簇上的氧化还原反应。第四组进行了过渡金属络合物催化的烯烃聚合、硅氢化等反应的从头算分子轨道研究。

项目成果

期刊论文数量（24）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

S.Sakaki,H.Satoh,H.Shono,Y.Ujino: "Ab Initio MO Study of the Geometry η^3⇔η^1 Conversion,and Reductive Elimination of a Palladium (II) η^3-Allyl Hydride Complex and Its Platinum (II) Analogue" Organometallics. 15・6. 1713-1720 (1996)

S.Sakaki、H.Satoh、H.Shono、Y.Ujino：“从头开始 MO 研究钯 (II) η^3-烯丙基氢化物配合物的几何 η^3⇔η^1 转换和还原消除其铂(II)类似物”有机金属学. 15・6. 1713-1720 (1996)

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Seiji Ogo, Takayoshi Suzuki, Yosiki Ozawa, and Kiyoshi Isobe: "Structures, Bonding and Reactivity of M-S-M' (M and M'=Rh, W,and Cu) Groups in Higher-Nuclearity Heterometallic Sulfide Clusters" Inorg.Chem.35. 6093-6101 (1996)

Seiji Ogo、Takayoshi Suzuki、Yosiki Ozawa 和 Kiyoshi Isobe：“高核异金属硫化物簇中 M-S-M（M 和 M=Rh、W 和 Cu）基团的结构、键合和反应性”Inorg.Chem.35。

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S.Ogo,T.suzuki,Y.Ozawa,K.Isobe: "Structures,Bonding,and Reactivity of M-S-M' (M and M'=Rh,W,and Cu) Groups in Higher-Nuclearity Heterometallic Sulfide Clusters" Inorganic Chemistry. 35・21. 6093-6101 (1996)

S.Ogo，T.suzuki，Y.Ozawa，K.Isobe：“高核异金属硫化物簇中 M-S-M（M 和 M=Rh、W 和 Cu）基团的结构、成键和反应性”无机化学35・21。6093-6101（1996）

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Z. Hou, K. Aida, Y. Takagi Y. Wakatsuki: "Synthesis and X-Ray Structure of the Divalent and Trivalent Ytterbium-Molybdenum Complexes Yb(II)(hmpa)_4(μ-OCMo(Co)_2Cp)_2 and (Yb(III)(hmpa)_5(μ-OCMo(CO)_2Cp)(CpMo(CO)_3)_2・THF" J. Organomet. Chem.487. C29-C29 (

Z. Hou、K. Aida、Y. Takagi Y. Wakatsuki：“二价和三价镱钼配合物 Yb(II)(hmpa)_4(μ-OCMo(Co)_2Cp)_2 的合成和 X 射线结构和(Yb(III)(hmpa)_5(μ-OCMo(CO)_2Cp)(CpMo(CO)_3)_2・THF" J. Organomet. Chem.487. C29-C29 (