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

• 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

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.

尽管最近对杯芳烃的研究兴趣浓厚，但对未改性杯芳烃的晚期过渡金属配合物知之甚少。本研究开发了杯芳烃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。至于芳烃组9金属配合物,反应[(cod) M(当地)2 (M = Rh, Ir)与杯[4]芳烃(LH4)的摩尔比0.5 - -0.6:1被发现给铑芳烃配合物(cod) M (LH3),虽然这在的摩尔比1.1 - -1.5:1 (M = Rh)导致的选择性形成双核的复合物[{(cod) Rh} 2 (LH2)]的Rh (cod) +片段之一是协调的芳基,另两个酚醛氧原子。后一种配合物的Rh-Ir杂双金属类似物的逐步合成也已实现。另一方面，用[Ph4P][ReOCI4]处理LHLi3，再用Ag2O氧化合成阴离子二氧合物[Ph4P][ReO2L] （LH4 = p- tbui -杯[4]芳烃）。[Ph4P][ReO2L]是第一个金属原子直接与杯芳烃体结合的杯芳烃铼配合物。更重要的是，[Ph4P][ReO2L]与溶剂化阳离子[Pd(C3H5)(Me2CO)x]+和[Rh(nbd)(Me2CO)x]+分别生成了杂双金属配合物[ReO2LPd(C3H5)]和[ReO2LRh(nbd)]。后一种配合物提供了在杯芳烃配体腔内具有异核过渡金属核的双核杯芳烃配合物的第一个例子。

项目成果

Y. Ishii, K. Onaka, H. Hirakawa, and K. Shiramizu: "Site-Selective and Stepwise Complexation of Two M(cod)+ (M = Rh, Ir)Fragments with Calix[4]arene"Chem. Commun.. 1150-1151 (2002)

Y. Ishii、K. Onaka、H. Hirakawa 和 K. Shiramizu：“两个 M(cod) (M = Rh, Ir) 片段与 Calix[4] 芳烃的位点选择性和逐步络合”Chem。