Preparation and Application of Multinuclear Organometal Complexes containing Group 10 Metals

含10族金属多核有机金属配合物的制备及应用

• 批准号: 15350058
• 负责人: KUROSAWA Hideo
• 金额: $ 9.86万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15350058/
• 关键词: cluster complex; group 10 metal; organometallic chemistry; クラスタ錯体

It is key to the development of new synthetic methods and creation of new materials to elucidate structure-reactivity relationship of organometallic complexes. The objective of this research project is the synthesis of multinuclear organometallic complexes of group 10 elements and elucidation of their structure and reactivities in order to establish new catalytic systems and creation of new materials based on the unique properties of the multimetallic complexes. The first result to be noted is clarification of the way of propagation of linear metallic aggregates bound to the π conjugated framework. Thus, the reaction of 1,4-diphenylbutadiene with hexakis(acetonitrile)dipalladium(I) gave dipalladium(I)-diphenylbutadiene sandwich complex A, which reacted further with Pd(0) complex to give tripalladium-diphenylbutadiene sandwich complex B. Then finally B reacted with another Pd(0) complex to afford tetrapalladium sandwich complex C. All of A-C were structurally characterized by X-ray analysis. The second remarkable result is concerned with complexation of Me_3SiOTf with Ni(0) complex containing π-coordinated C=C and C=O groups which triggered the oxidative cyclization of the Ni(0) complex to afford 5-membered oxa-nickelacycle compound. This would shed light on the mechanism of nickel catalyzed 3-component coupling reactions involving olefin, carbonyl and organometallics.

阐明有机金属配合物的结构-反应性关系是开发新合成方法和创造新材料的关键，本研究项目的目的是合成第10族元素的多核有机金属配合物并阐明其结构和反应性。为了基于多金属配合物的独特性质建立新的催化系统并创造新材料，第一个值得注意的结果是阐明了多金属络合物的传播方式。因此，1,4-二苯基丁二烯与六(乙腈)二钯(I)反应得到二钯(I)-二苯基丁二烯夹心络合物A，其进一步与Pd(0)络合物反应生成。得到三钯-二苯基丁二烯夹心络合物B。最后B与另一个Pd(0)络合物反应得到四钯所有 A-C 均通过 X 射线分析进行了结构表征。第二个显着结果涉及 Me_3SiOTf 与含有 π 配位 C=C 和 C=O 基团的 Ni(0) 络合物的络合，引发了 A-C 的氧化环化。 Ni(0) 配合物提供 5 元氧杂镍环化合物，这将有助于揭示镍催化的三组分偶联反应烯烃的机理。羰基和有机金属化合物。

项目成果

Synthesis, Structure, and Reactivity of η^3-1-Hydroxyallyl Complex : Protonation of an α,β-Unsaturated Carbonyl Compound Bound to Pd(0) and Pt(0)

η^3-1-羟基烯丙基配合物的合成、结构和反应性：与 Pd(0) 和 Pt(0) 结合的 α,β-不饱和羰基化合物的质子化

• 发表时间: 2003
• 期刊: J.Am.Chem.Soc. 125
• 作者: 生越専介;黒沢英夫;森田将基
• 通讯作者: 森田将基

Stepwise growth of polypalladium chains in 1,4-diphenyl-1,3-butadiene sandwich complexes

• DOI: 10.1039/b403098b
• 发表时间: 2004-06-21
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Tatsumi, Y;Naga, R;Kurosawa, H
• 通讯作者: Kurosawa, H

Perylene-tetrapalladium sandwich complexes.

• DOI: 10.1021/ja0358246
• 发表时间: 2003-06
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Tetsuro Murahashi;Tomohito Uemura;H. Kurosawa

Synthesis, Structure and Reactivity of η^3-1-Hydroxyallyl Complex : Protonation of α,β-Unsaturated Carbonyl Compound Bound to Palladium(0) and Platinum(0).

η^3-1-羟基烯丙基配合物的合成、结构和反应性：与钯(0) 和铂(0) 结合的α,β-不饱和羰基化合物的质子化。

• 发表时间: 2003
• 期刊: J.Am.Chem.Soc. 125
• 作者: Sensuke Ogoshi;Masaki Morita;Hideo Kurosawa
• 通讯作者: Hideo Kurosawa

From mononuclear to multinuclear complexes of palladium containing unsaturated hydrocarbon ligands

• DOI: 10.1016/j.jorganchem.2004.08.005
• 发表时间: 2004-11
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: H. Kurosawa