Synthesis and Metal‐Binding Properties of Polybipyridine Ligands Derived from Acyclic and Macrocyclic Polyamines

Abstract

Abstract Synthetic procedures have been developed for the preparation of ligands bearing two to six pendent, unsubstituted or substituted 2, 2′‐bipyridine groups attached to acyclic (tripode, tetrapode) and macrocyclic (triazanonade‐cane, cyclam, hexacyclen, bis(bipyrido)hexaazamacrocycle) polyamines. Ligands 1‐5 have been obtained in high yield by condensation of 6‐(bromomethyl)‐2, 2′‐bipyridine ( 9b ) with the corresponding amines in the presence of NaOH, H 2 O, and MeOH. Ligands 6‐8 have been prepared in good yield by condensation of 9b or the di‐ or tetrasubstituted mono (bromomethyl) bipyridine 10b or 11b , respectively, with the corresponding amines in the presence of Na 2 CO 3 and MeCN. Ligand 1 forms hemi‐cage complexes with Ru II , Fe I , Cr II , and Cr III cations and trinuclear complexes with [RuCl 2 (bpy) 2 ] and [ReCl(CO) 5 ]. Tetrapode 2 and hexapode 4 gave tetranuclear and dinuclear complexes, respectively, by reaction with Fe11 salts. These complexes possess a variety of interesting physical and chemical properties.