High molecular weight poly(ethylene glycol) (PEG) derivatized iron tris(bipyridine) complexes, presenting hydroxyl end groups for further modification as bioconjugates, copolymers, or cross-linking agents, were synthesized via ring-opening anionic polymerization of ethylene oxide from hydroxyl-functionalized bipyridine (bpy) initiators and subsequent chelation to iron(II). Bpy-centered PEG macroligands (bpyPEG(2)) with molecular weights ranging from 4000 to 17 000 and low polydispersity indices (< 1.1) were obtained. Chelation of the bpyPEG(2) macroligands to iron(II) sulfate was studied in aqueous solution by titration and kinetics experiments, which revealed unexpected air sensitivity compared to nonpolymeric iron tris(bipyridine) complexes. Red-violet aqueous solutions of [Fe(bpyPEG(2))(3)](2+) begin to bleach within hours when exposed to air. Enhanced polymer degradation and gel formation of acrylate-modified bpyPEG2 in the presence of Fe2+ suggest that radicals may be involved. Under argon, the chromophores are stable. Polymeric iron complexes are slower to form and faster to degrade in air with increasing bpyPEG2 molecular weight. These studies demonstrate the influence of molecular weight in polymeric iron tris(bipyridine) complex coordination chemistry and reactivity.