Silicon bridges ferrocenophanes, ring-opening polymerization

RING-OPENING POLYMERIZATION OF SILICON-BRIDGED [1]FERROCENOPHANES... 

B. Synthesis, Properties, and Ring-Opening Polymerization of Silicon-Bridged 1 ]Ferrocenophanes... 

Prior to 1992 no efforts to prepare polymers with main chains consisting of ferrocene and organosilane units via ring-opening methods had been reported. The first developments in this area involved attempts to polymerize silicon-bridged ferrocenophanes and related species (23,41). The first successful ROPs involved the use of [l]silaferrocenophanes as cyclic monomers, and the progress in this area to date together with relevant previous work is now reviewed. 

The discovery of the anionic ring-opening polymerization of silicon-bridged[l]ferrocenophanes enabled the synthesis of well-defined, near-monodisperse poly(ferrocenylsilane) homo- and block copolymers. PFS was combined with polystyrene [38], polyisoprene [39], poly(dimethylsilox-ane) [40], poly(ethylene oxide) [41], poly(ferrocenylphenylphosphine) [42], poly(aminoalkyl methacryate) [43] and recently with poly(methyl methacrylate) [44,45] blocks. 

Cyclic, silicon-bridged [l]ferrocenophanes have been found to undergo thermal ring-opening polymerization to afford high-molecular-wei t poly(ferrocenylsilane)s (see Eq. 1.31) [8, 43]. Many other members of this family of polymers are now known including those where the silicon center is replaced by Sn(IV), P(III), Ge(IV), B(III) etc., [8],... 

The relief of ring-strain present in silicon-bridged ferrocenophanes can be utilized as the driving foree for its ring-opening polymerization (ROP). Manners and coworkers have shown that it is possible to induce the ROP of silicon-bridged ferrocenophanes by at least three different synthetic approaches [3,7,44-46], These are (a) thermal ROP (b) anionic ROP and (c) transition-metal-complex eatalyzed ROP. 

Thermal Ring-opening Polymerization of Silicon-bridged Ferrocenophanes... 

Temple K, JaMe F, Sheridan JB, Manners 1 (2001) The nature of the active catalyst in late transition metal-mediated ring-opening polymerization (ROP) reactions mechanistic studies of the platinum-catalysed ROP of silicon-bridged [l]ferrocenophanes. J Am Chem Soc 123 1355-1364... 

Bartle-Scott A, Resendes R, Manners I (2003) Transition metal-catalyzed ring-opening polymerization of silicon-bridged [l]ferrocenophanes in the presence of functional silanes molecular weight control and synthesis of telechelic poly(ferrocenylsilanes). Macromol Chem Phys 204 1259-1268... 

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. 

The transition-metal-catalyzed ring-opening polymerization of silicon-bridged, strained, ring-tilted ferrocenophans yields polyferrocenylsilanes with intriguing properties. ... 

Rulkens R, Ni Y, Lough AJ, Manners I (1994) Anionic ring-opening oligomerization and polymerization of silicon-bridged [l]ferrocenophanes characterization of short-chain models for poly(ferrocenylsilane) high polymers. J Am Chem Soc 116 797-798... 

Transition metal-catalyzed ring-opening co-polymerization of silicon-bridged [l]-ferrocenophanes 496... 

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