Ferrocenes ring-opening polymerization

Germanium-bridged [l]ferrocenophanes undergo a number of ring-opening polymerization reactions to yield ferrocene-containing polymers, and the versatility of this interconversion has been reviewed. A -GeMe2-... 

Rauchfuss appears to have been the first to report a ring-opening polymerization that incorporates the ferrocene units into a polymer backbone.14 Monomer 6.17 reacts at room temperature with tributylphosphine to yield polymer 6.18 via a desulfurization process as shown in reaction (7). 

Strained silyl-bridged ferrocenes add to Pt°. This is the key reaction in the Pt catalyzed ring-opening polymerization of these ansa-ferrocenes 87... 

The earliest and most well-developed route to polyphosphazenes involves the thermal ring-opening polymerization of cyclic phosphazenes bearing halogen substituents at phosphorus. Use of this method and subsequent halogen replacement with alkoxides has led to the synthesis of ferrocene- and ruthenocene-containing polyphosphazenes (2.20 and 2.21) with molecular weights (M ) in excess of 2 x 10 [49, 50]. 

Ferrocene has also been incorporated in zeolite hosts [244, 255] and hydrocarbon loss on heating and oxidation to ferricinium cation were observed. Similarly, substituted ruthenocenes were also investigated [256, 257]. The ring opening polymerization of a [l]silaferrocenophane within the channels of mesoporous silica (MCM-41) gave precursors of magnetic iron nanostructures [257a,b]. 

As will be shown in the next section, strained ferrocenophanes can be used as monomers for ring-opening polymerization to afford ferrocene-containing polymers. 

Recently, high molecular ferrocene polymers have been prepared by a ring opening polymerization as shown in eqs. (15.39)-( 15.40) [96-97c]. 

Ring opening polymerization of propylene sulphide by l,r-dimercapto ferrocene yields polymers t luch contain one ferrocene unit in the center of the macromolecule (Scheme 15.12). 

Ferrocenes are key components of polymers. For instance. Manners disclosed remarkable ring-opening polymerization of ferrocenophanes (below). - Ferrocene-containing polymers have also been synthesized using classic routes by... 

Gomez-Elipe, P., Resendes, R., Macdonald, P.M., and Manners, I. (1998) Transition metal catalyzed ring-opening polymerization (ROP) of silicon-bridged [l]ferrocenophanes facile molecular weight control and the remarkably convenient synthesis of poly(ferrocenes) with regioregular, comb, star, and block architectures. Journal of the American Chemical Society, 120,8348. 

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