Abstract
The silicon-bridged [1]ferrocenophanes Fe(η-C5H4)2SiRR‘ [3 (R = Me, R‘ = Cl), 4 (R = R‘ = Cl)] with chlorine substituent(s) at silicon were prepared via the reaction of Fe(η-C5H4Li)2·TMEDA (TMEDA = tetramethylethylenediamine) with the chlorinated silanes MeSiCl3 and SiCl4, respectively. An X-ray diffraction study of 4 indicated that the cyclopentadienyl rings in this species are tilted by an angle of 19.2(4)°, typical of other structurally characterized silicon-bridged [1]ferrocenophanes. Thermal ring-opening polymerization (ROP) of 3 and 4 at 250 °C yielded the first high molecular weight poly(ferrocenylsilanes) with halogen substituents at silicon, [Fe(η-C5H4)2SiRR‘]n [7 (R = Me, R‘ = Cl), 8 (R = R‘ = Cl)]. Transition-metal-catalyzed polymerization of 3 and 4 with Pd and Pt catalysts also yielded polymers 7 and 8 in solution at room temperature. Polymer 7 was soluble in polar organic solvents and was characterized by 1H, 29Si, and 13C NMR and elemental analysis. In contrast, poly(ferrocenylsilane) 8 was found to be insoluble in organic solvents and this material was characterized by elemental analysis and derivatization. Substitution of the chlorine side groups in polymer 7 was achieved under mild conditions via reaction with the organolithium reagents MeLi, PhLi, and LiC⋮C(CH2)4H to afford the known polymers [Fe(η-C5H4)2SiMe2]n (2a) and [Fe(η-C5H4)2SiMePh]n (2d) and the new polymer [Fe(η-C5H4)2SiMeC⋮C(CH2)4H]n (9), respectively. The molecular weights for the completely halogen-substituted poly(ferrocenylsilanes) 2a, 2d, and 9 were estimated by gel permeation chromatography in THF to be in the range of Mw = 7.4 × 104 to 1.7 × 105 and Mn = 3.6 × 104 to 1.1 × 105 versus polystyrene standards. Substitution of the chlorine atoms in 8 was also demonstrated by reaction of the polymer with MeLi to give 2a.
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