Transformation of alkene feedstocks to alkyl halide monoadducts through atom transfer radical addition (ATRA) reactions, leads to the production of attractive molecules with well-defined compositions, architectures, and functionalities. For ideal ATRA reactions, incorporating active catalysts and fast initiators, the activation step occurs too quickly to be monitored by common instrumentation, rendering direct measurement of the activation rate constant (kact) very difficult, if not impossible. Herein, we outline a method that can be used to calculate (kact) values in reactions that incorporate highly active copper complexes with fast initiators. This was achieved utilizing modified tris(2-(amino)ethyl)amine [TREN] based ligands that can generate copper complexes capable of slowing down the activation process to allow monitoring by UV/Vis spectroscopy. The activation process was isolated from the deactivation step and possible side reactions (termination / polymerization) by employing the radical trapping agent 2,2,6,6-Tetramethyl-1-piperidinyloxy [TEMPO]. Subsequently, pseudo-first order kinetic conditions were created which were used to calculate corresponding activation rate constant (kact) values.

Utilizing TREN-based copper complexes to calculate activation rate constant values in ideal atom transfer radical addition (ATRA) reactions

249th National Meeting (2015)

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