Organometallic polymers. I. Synthesis of ferrocene-containing poly(phosphine oxides) and poly(phosphine sulfides)

Poly(phosphine oxides) and poly(phosphine sulfides) of ferrocene were synthesized in the melt phase. The resulting ferrocene polymers, linked by phosphorus bridges, were thermally stable and infusible solids, of low molecular weight (M?_n < 4000). Phenyldichlorophosphine, phenyldichlorophosphonate, and phenylphosphonothioic dichloride were copolymerized with ferrocene in the melt phase (80–110°C.) with ZnCl₂ as a catalyst. As the polymerization temperature was raised, cleavage of cyclopentadiene rings from iron became more pronounced, and cyclopentane-bridged polymers of ferrocene were produced in competition with the ferrocene–phosphorus polymers. The cleavage-polymerization process became predominant at 140°C. The structures of poly(phosphine oxides) (and sulfides) of ferrocene were verified by infrared and nuclear magnetic resonance spectroscopy.