Monomers, oligomers and polymers containing arenes with pendent transition metal moieties

A number of synthetic routes have been utilized in the production of organometallic monomers and polymers containing arenes coordinated to the Group VI, VII and VIII transition metals. Transition metal-coordinated monomers were prepared either by nucleophilic aromatic substitution reactions of transition metal-coordinated haloarenes with phenolic compounds or via ligand exchange reactions. These monomers were polymerized directly or following removal of the metallic moieties to produce the resulting organometallic or organic polymers. Well-defined oligomeric ethers prepared via sequential nucleophilic displacement reactions were functionalized via nucleophilic addition reactions. The synthesis and characterization of heterometallic oligomers and complexes containing both neutral and cationic metallic moieties are also reviewed. The synthesis of polymers containing arenes coordinated to transition metal moieties was investigated using metal-mediated reactions. The introduction of transition metal moieties into pre-existing polymeric materials has also proven to be an effective methodology to isolate this class of organometallic polymer. Supramolecular assembly of arene complexes of transition metals was explored as a route to macromolecular materials. The use of arene complexes has allowed for the preparation of a number of polyfunctional molecules used in the design of dendrimers and star polymers.