Tuesday, July 10, 2012


Catalyzation of Copper in TMC ATRA/ATRP
Trischler, Aaron; Oshin, Kayode; Pintauer, Tomislav
Department of Inorganic Chemistry
Duquesne University

The structure and mechanistic study of transition metal catalyzed atom transfer radical addition or polymerization (TMC ATRA/ATRP) reactions is a growing field of inorganic chemistry. They involve the formation of new carbon-carbon bonds through the addition of a saturated poly-halogenatyed hydrocarbon to an alkene, usually catalyzed by a transition metal complex. In this study, we set out to examine the structural, electrochemical, and kinetic behavior of eight unique copper complexes that have the predisposition to be used as catalysts in ATRA or ATRP reactions. Complexation reactions were carried out to generate the following; [Cu(I)(TREN-B)][Cl], [Cu(I)(TREN-4CB)][Cl], [Cu(I)(TREN-4MB)][Cl], [Cu(I)(TREN-4TFB)][Cl], [Cu(II)(TREN-B)][Cl2], [Cu(II)(TREN-4CB)][Cl2], [Cu(II)(TREN-4MB)][Cl2], and [Cu(II)(TREN-4TFB)][Cl2]. Characterizations were carried out used infrared, NMR, and mass spectroscopy. Solid state and electrochemical characterizations were carried out using x-ray crystallography and cyclic voltammetry respectively. Kinetic studies were conducted using UV/Vis spectrometry with carbon tetrachloride as the alkyl halide and (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO) as the radical trapping agent. This allowed for the kinetic isolation of the activation process in the ATRP reaction and helped us calculate the activation rate constants (kact) for the respective copper complexes.

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