Metallomacrocycles with a Difference: Macrocyclic Complexes with Exocyclic Ruthenium(II)‐Containing Domains |
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Authors: | Edwin C. Constable Prof. Dr. Catherine E. Housecroft Prof. Dr. Markus Neuburger Pirmin J. Rösel Dr. Silvia Schaffner Dr. Jennifer A. Zampese Dr. |
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Affiliation: | Department of Chemistry, University of Basel, Spitalstrasse 51, 4056 Basel (Switzerland), Fax: (+41)?61‐267‐1018 |
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Abstract: | 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. |
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Keywords: | chirality heterocycles macrocycles ruthenium supramolecular chemistry |
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