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Tailored synthesis of complexes and polymers containing organoiron and organocobalt Winram, Diana Joyce

Abstract

This thesis describes synthetic strategies for the incorporation of organoiron and organocobalt into polymers. Norbornene and methacrylate based polymers which contained μ-alkyne-bis(tricarbonylcobalt) complexes and either η⁶-(haloarene)-η⁵-cyclopentadienyliron(II) hexafluorophosphate or ferrocene moieties were synthesized. Norbornene monomers which contained both the organoiron and the organocobalt complexes were successfully polymerized using ring opening metathesis polymerization. Radical polymerization of methacrylate monomers which contained η⁶-(haloarene)-η⁵-cyclopentadienyliron(II) hexafluorophosphate moieties and alkyne functional groups, allowed for the coordination of dicobalt hexacarbonyl post polymerization. The monomers and their precursors were characterized through nuclear magnetic resonance spectroscopy, infrared spectroscopy and cyclic voltammetry. The molecular weights of the polymers were estimated using gel permeation chromatography and the thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry. Another class of organoiron monomers containing alkyne functional groups were polymerized through condensation of their η⁶-(haloarene)-η⁵-cyclopentadienyliron(II) hexafluorophosphate moieties with various dithiols. A monomer which contained both η⁶-(haloarene)-η⁵-cyclopentadienyliron(II) hexafluorophosphate and μ-alkyne-bis(tricarbonylcobalt) moieties was also combined with various dithiol linking groups. Preliminary studies on the synthesis and characterization of three siloxane based polymers which contained η⁶-(arene)-η⁵-cyclopentadienyliron(II) hexafluorophosphate moieties were also explored.

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