This study examines the structural, electrochemical, and kinetic behavior of eight unique copper complexes that have the predisposition to be used as catalysts in atom transfer radical reactions. The tetradentate ligand, tris-(2-aminoethyl)amine (TREN), was synthesized and the ligand electronics were modified through incorporatation of different functional groups in the para position of the phenyl group. Four copper(I) and four copper(II) complexes with different TREN ligands were prepared and characterized using infrared and NMR spectroscopy as well as mass spectrometry. Solid state and electrochemical characterizations were executed using X-ray crystallography and cyclic voltammetry, respectively. Kinetic studies were conducted using UV-vis spectroscopy with carbon tetrachloride, an alkyl halide, and radical trapping agent (2, 2, 6, 6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO). This allowed for kinetic isolation of the activation process in atom transfer radical addition (ATRA) and provided the parameters needed to calculate the activation rate constants (kact) for each copper complex.

Synthesis, characterization, and kinetic study of copper tris(2-aminoethyl)amine complexes containing para-substituted functional groups

245th National Meeting (2013)

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