- Electroorganic reactions. Part 55. Quinodimethane chemistry. Part 3. Transition metal complexes as inter- and intra-molecular redox catalysts for the electrosynthesis of poly(p-xylylene) (PPX) polymers and oligomers
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The role of metal complexes as redox mediators in the electrosynthesis of poly(p-xylylenes) (PPXs) has been explored, with a view to designing metal-containing precursors that can act both as mediators and starting materials for metal-containing polymers. A number of transition metal complexes [Cr(III), Ni(II) and Co(II)] are efficient redox catalysts for production of quinodimethanes, and hence PPXs. Following encouraging results from experiments using mediators based on anthranilic acid and salicylaldehyde ligands a macrocyclic compound was designed, and successfully prepared by a convergent route that incorporated both a 1,4-bis(chloromethylarene) function as a precursor to a quinodimethane and a Ni(II) salen unit as an intramolecular redox catalyst. The macrocycle was successfully reduced cathodically to yield a PPX polymer with bound Ni(II). Evidence is presented for the operation of intramolecular redox catalysis (homomediation).
- Janssen,Utley,Carre?,Simon,Schirmer
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p. 1573 - 1584
(2007/10/03)
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