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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

基本信息

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

项目摘要

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-活性关系是开发新的合成方法和创造新材料的关键。本研究的目标是合成10族元素的多核有机金属配合物，并阐明其结构和反应活性，以期根据多金属配合物的独特性质建立新的催化体系和创造新的材料。需要注意的第一个结果是澄清了束缚在π共轭框架上的线性金属聚集体的传播方式。因此，1，4-二苯基丁二烯与六(乙腈)双钯(I)反应生成双钯(I)-二苯基丁二烯夹心络合物A，再与Pd(0)络合物反应得到三钯-二苯基丁二烯夹心络合物B，最后B与另一Pd(0)络合物反应得到四钯夹心络合物C。第二个显著的结果与Me_3SiOTf与含有π配位的C=C和C=O基团的Ni(0)络合物的络合作用有关，它触发了Ni(0)络合物的氧化环化反应，生成了五元氧镍环化合物。这将有助于揭示镍催化的烯烃、羰基和金属有机化合物三组分偶联反应的机理。