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.

尽管最近对金属钙烯烯的兴趣却很少以未修饰的钙棒烯的晚过渡金属复合物而闻名。在这项研究中，我们开发了用于钙棒烯的7-10组过渡金属衍生物的合成方法，并揭示了它们独特的反应性。至于卡利克利烯组9金属络合物，[（cod）M（ome）] 2（m = rh，ir）与钙[4]领域（LH4）的摩尔比为0.5-0.6：1的反应已发现rhodium arene复合物[（cod）m（cod）m（lh3）]，同时在1.1-1-1-1-1-1的反应。 Dinuclear复合物[{（COD）RH} 2（LH2）]，其中一个RH（COD）+片段由芳基组协调，另一个由两个酚氧原子协调。也已经实现了后一种复合物的Rh-IR异数字类似物的逐步合成。另一方面，通过用[ph4p] [reoci4]处理LHLI3，合成了阴离子二氧化氢复合物[PH4P] [PH4P] [REO2L]（LH4 = P-TBU-CALIX [4] ARENE），然后用AG2O氧化。 [PH4P] [REO2L]是Calixarene rhenium络合物，其中金属原子直接与钙棒核体结合。更重要的是，[PH4P] [REO2L]与溶剂化的阳离子物种[Pd（C3H5）（ME2CO）X]+和[RH（NBD）（ME2CO）X]+反应，以提供杂的金属复合物[REOO2LPD（C3H5）]和[REO2LRH（REO2LRH（NBD）]。后者的复合物提供了二核钙济钙甲硅烷基络合物的第一个例子，该复合物在calixarene配体的腔体内具有异质核过渡金属芯。