Site-Selective and Stepwise Complexation of Transition Metal Fragments on Calixarene and Functions of Polynuclear Calixarene Complexes

过渡金属片段在杯芳烃上的位点选择性逐步络合及多核杯芳烃配合物的功能

基本信息

批准号：
13650899
负责人：
ISHII Youichi
金额：
$ 2.62万
依托单位：
CHUO UNIVERSITY (2002)The University of Tokyo (2001)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650899/
关键词：
Calixarene rhodium iridium rhenium ruthenium palladium heterometallic complexes ヘテロ二核錯体

项目摘要

In spite of the recent interest in metallocalixarenes little is known for late transition metal complexes of unmodified calixarenes. In this study we have developed the synthetic methods for group 7-10 transition metal derivatives of calixarenes and revealed their unique reactivities. As for the calixarene group 9 metal complexes, the reaction of [(cod)M(Ome)]2 (M = Rh, Ir) with calix[4]arenes (LH4) in the molar ratio of 0.5-0.6: 1 has been found to give the rhodium arene complexes [(cod)M(LH3)], while that in the molar ratio of 1.1-1.5:1(M = Rh) leads to the selective formation of the dinuclear complexes [{(cod)Rh}2(LH2)] in which one of the Rh(cod)+ fragments is coordinated by an aryl group and the other by two phenolic oxygen atoms. The stepwise synthesis of the Rh-Ir heterobimetallic analogue of the latter complex has also been achieved. On the other hand, the anionic dioxorhenium complex [Ph4P][ReO2L] (LH4 = p-tBu-calix[4]arene) is synthesized by treatment of LHLi3 with [Ph4P][ReOCI4] followed by oxidation with Ag2O. [Ph4P][ReO2L] is the first calixarene rhenium complex in which the metal atom is directly bound to the body of calixarene. More importantly, [Ph4P][ReO2L] reacts with solvated cationic species [Pd(C3H5)(Me2CO)x]+ and [Rh(nbd)(Me2CO)x]+ to afford the heterobimetallic complexes [ReO2LPd(C3H5)] and [ReO2LRh(nbd)], respectively. The latter complexes provide the first examples of dinucelar calixarene complexes which possess a heterodinuclear transition metal core inside the cavity of a calixarene ligand.

尽管最近人们对金属局部芳烃感兴趣，但对未改性杯芳烃的后过渡金属配合物知之甚少。在这项研究中，我们开发了杯芳烃第7-10族过渡金属衍生物的合成方法，并揭示了它们独特的反应活性。对于杯芳烃第 9 族金属配合物，[(cod)M(Ome)]2 (M = Rh, Ir) 与杯[4]芳烃 (LH4) 以 0.5-0.6:1 的摩尔比反应。发现得到铑芳烃络合物[(cod)M(LH3)]，而摩尔比为1.1-1.5:1(M = Rh)时会得到选择性形成双核配合物 [{(cod)Rh}2(LH2)]，其中一个 Rh(cod)+ 片段由芳基配位，另一个由两个酚氧原子配位。后一种配合物的Rh-Ir异双金属类似物的逐步合成也已实现。另一方面，阴离子二氧铼配合物[Ph4P][ReO2L]（LH4 = p-tBu-calix[4]芳烃）是通过用[Ph4P][ReOCI4]处理LHLi3，然后用Ag2O氧化来合成的。 [Ph4P][ReO2L]是第一个杯芳烃铼配合物，其中金属原子直接与杯芳烃主体结合。更重要的是，[Ph4P][ReO2L]与溶剂化阳离子物质[Pd(C3H5)(Me2CO)x]+和[Rh(nbd)(Me2CO)x]+反应，得到异双金属配合物[ReO2LPd(C3H5)]和[ ReO2LRh(nbd)]，分别。后者配合物提供了双核杯芳烃配合物的第一个例子，其在杯芳烃配体的空腔内具有异双核过渡金属核。