Department of Chemistry, University of Basel, Spitalstrasse 51, 4056 Basel, Switzerland.
Chemistry. 2009 Nov 2;15(43):11746-57. doi: 10.1002/chem.200901640.
The templated synthesis of organic macrocycles containing rings of up to 96 atoms and three 2,2'-bipyridine (bpy) units is described. Starting with the bpy-centred ligands 5,5'-bis[3-(1,4-dioxahept-6-enylphenyl)]-2,2'-bipyridine and 5,5'-bis[3-(1,4,7-trioxadec-9-enylphenyl)]-2,2'-bipyridine, we have applied Grubbs' methodology to couple the terminal alkene units of the coordinated ligands in [FeL3]2+ complexes. Hydrogenation and demetallation of the iron(II)-containing macrocyclic complexes results in the isolation of large organic macrocycles. The latter bind {Ru(bpy)2} units to give macrocyclic complexes with exocyclic ruthenium(II)-containing domains. The complex [Ru(bpy)2(L)]2+ (isolated as the hexafluorophosphate salt), in which L=5,5'-bis[3-(1,4,7,10-tetraoxatridec-12-enylphenyl)]-2,2'-bipyridine, undergoes intramolecular ring-closing metathesis to yield a macrocycle which retains the exocyclic {Ru(bpy)2} unit. The poly(ethyleneoxy) domains in the latter macrocycle readily scavenge sodium ions, as proven by single-crystal X-ray diffraction and atomic absorption spectroscopy data for the bulk sample. In addition to the new compounds, a series of model complexes have been fully characterized, and representative single-crystal X-ray structural data are presented for iron(II) and ruthenium(II) acyclic and macrocyclic species.
本文描述了一种模板合成含有多达 96 个原子和三个 2,2'-联吡啶（bpy）单元的有机大环的方法。以 bpy 为中心的配体 5,5'-双[3-(1,4-二氧杂庚-6-烯基)苯基]-2,2'-联吡啶和 5,5'-双[3-(1,4,7-三氧杂十九-9-烯基)苯基]-2,2'-联吡啶为起始原料，我们应用 Grubbs 方法将配位配体中的末端烯烃单元在 [FeL3]2+ 配合物中进行偶联。铁(II)含大环配合物的氢化和脱金属化导致大环的分离。后者将 {Ru(bpy)2} 单元结合到具有外接钌(II)含域的大环配合物中。[Ru(bpy)2(L)]2+（分离为六氟磷酸盐盐），其中 L=5,5'-双[3-(1,4,7,10-四氧杂十三-12-烯基)苯基]-2,2'-联吡啶，经历分子内环 closing metathesis 以得到保留外接 {Ru(bpy)2} 单元的大环。后者大环中的聚（乙二氧基）域很容易捕获钠离子，这一点已通过单晶 X 射线衍射和原子吸收光谱数据得到证实。除了新化合物外，还对一系列模型配合物进行了充分的表征，并为铁(II)和钌(II)无环和大环物种提供了代表性的单晶 X 射线结构数据。
