Ring-opening polymerization of [1]metallocenophanes: A route to organometallic polymeric micelles, ionomeric poly(ferrocenes) and other systems of interest

Silicon-bridged [1]- and [2]ferrocenophanes with trimethylsilyl substituents on the cyclopentadienyl rings have been synthesized. The latter compound was studied by single crystal X-ray diffraction and was found to possess a larger tilt angle (5.4(6)°) than the analogous non-substituted species. No ring-opening polymerization (ROP) was observed even at elevated temperatures. The [1]ferrocenophane did polymerize readily and yielded very soluble, high molecular weight poly(ferrocenylsilane).; A series of high molecular weight poly(ferrocenylgermanes) was synthesized via the thermal ROP of germanium-bridged, [1]ferrocenophanes. Poly(ferrocenyldimethylsilane)poly(ferrocenyldimethylgerinane) random copolymers could be synthesized via ROP both thermally and in the presence of a transition metal catalyst. The thermal transition and electrochemical behaviour, and morphology of the resultant polymers were examined by differential scanning calorimetry (DSC), cyclic voltammetry and wide-angle X-ray scattering and were found to be similar to the analogous poly(feffocenylsilanes).; The first stable phosphonium-bridged [1]ferrocenophane was synthesized and was found to undergo both thermal and transition metal-catalyzed ROP. The resultant ionomeric polymer was soluble in highly polar solvents (e.g. acetone) but displayed only limited stability. A DSC study of the glass transition temperatures of a series of methylated poly(ferrocenylphenylphosphines) of known molecular weight suggested that the molecular weight of the transition metal-catalyzed ROP product was greater than 46 000 and the thermally produced polymer was of even higher molecular weight.; The first living anionic ROP of phosphorus-bridged [1]ferrocenophanes was achieved, allowing access to poly(ferrocenylphosphine) homopolymers and block copolymers with controlled architectures. The aggregation behaviour of poly(ferrocenylphenylphosphine)-bpoly(dimethylsiloxane) in a non-solvent (hexane) for the poly(ferrocenylphosphine) block was examined by dynamic light scattering and by transmission electron microscopy and atomic force microscopy after solvent evaporation. The most commonly observed morphology was spheres although other morphologies were also observed. Preliminary metal coordination studies were also conducted.; Spirocyclic [1]zirconocenophanes were synthesized and found to undergo transition metal-catalyzed ROP.