Coordination of dicobalt hexacarbonyl to the alkyne moiety of norbornene complexes containing either ferrocene or η(6) -chlorobenzene-η(5) -cyclopentadienyliron hexafluorophosphate, gave two unique trimetallic complexes available for ROMP. Polymerization of each monomer using Grubbs second generation catalyst gave organoiron/organocobalt polynorbornenes with weight average molecular weights between 55 300 and 69 000 with PDIs between 1.2 and 1.9. Cyclic voltammetric studies of the monomers and polymers at -40 °C showed a reversible reduction for cationic complexes containing η(6) -benzene-η(5) -cyclopentadienyliron and for the dicobalt hexacarbonyl moieties while, a reversible oxidation for the ferrocene containing complex was observed. Thermal analysis showed that the cobalt carbonyl moiety of the polymers degraded near 130 °C; however, the polymeric backbone was stable up to 350 °C. Scanning electron microscopy (SEM) and SEM-EDS indicated that the polymers possessed a fine globular morphology and that the distribution of iron and cobalt atoms was homogenous on the macro-scale.
Radical polymerization of organoiron (alkynyl methacrylate)s afforded a series of organoiron poly(alkynyl methacrylate)s with the ability to coordinate dicobalt hexacarbonyl. The polymers were post-modifi ed with dicobalt hexacarbonyl moieties through reaction with dicobaltoctacarbonyl. Gel permeation chromatography indicated that the polymers possessed weight average molecular weights between 17 800 Da and 33 900 Da with PDIs between 1.3 and 1.6. Thermal analysis revealed that the polymers possess glass transition temperatures between 78 and 138 ° C.
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