Redox Initiated Cationic Polymerization: Silane-N-Aryl Heteroaromatic Onium Salt Redox Couples

In this article, a new route for the synthesis of N-aryl heteroaromatic onium salts by the direct copper catalyzed arylation of pyridine, substituted pyridines, isoquinoline, and acridine with diaryliodonium salts is described. It was demonstrated that these N-aryl heteroaromatic onium salts undergo facile platinum or rhodium-catalyzed reduction by silanes bearing Si-H groups. The reduction of N-aryl heteroaromatic onium salts generates Bronsted acids. When this redox reaction was carried out in situ in the presence of an appropriate monomer, cationic polymerization was observed. Using this approach, the cationic polymerizations of epoxides, oxetanes, 1,3,5-trioxane, styrene, and vinyl ethers were carried out. The use of optical pyrometry to monitor the redox initiated cationic polymerizations of some representative multifunctional monomers is described. (C) 2010 Wiley Periodicals, Inc. J PolymSci Part A: Polym Chem 48: 4484-4495, 2010