1. 600 Forbes Avenue, 308 Mellon Hall, Pittsburgh, PA 15282
Development of Transition Metal Catalysts for Radical (Co)Polymerization of Nonpolar Olefins and Polar Monomers
Tomislav Pintauer, Department of Chemistry and Biochemistry, Duquesne University
600 Forbes Avenue, 308 Mellon Hall, Pittsburgh, PA 15282
The main objective of our project is to rationally develop catalytic systems that can be used in radical copolymerization of olefins and polar monomers based on changing reactivity ratios through complexation of the monomers with copper(I) complexes.
Copper(I)/2,2’-bipyridine complexes, [CuI(bpy)(π-CH2CHCOOCH3)][A] (A = CF3SO3-, ClO4- and PF6- have been synthesized and characterized. These complexes are used in copper(I) mediated cyclopropanation and aziridination reactions of methyl acrylate and represent the first class of trigonal pyramidal copper(I) complexes with π-coordinated electron poor olefins. In the case of CF3SO3- and PF6- complexes, weak coordination of the counterion was observed. The counterion ClO4- was noncoordinating in the copper(I) complex, which was dimeric in the solid state with the oxygen atoms of the carbonyl moieties in methyl acrylate bridging two copper(I) centers. The reactivity of coordinated methyl acrylate is currently being investigated in free radical polymerization reactions.
[CuI(2,2’-bpy)(-MA)][A] Complexes