Atom transfer radical reactions of haloalkanes and α-halocarbonyls to α-olefins have emerged as some of the most atom economical methods for simultaneously forming C–C and C–X bonds, leading to the production of more attractive molecules with well-defined compositions, architectures, and functionalities. Halide functionality incorporated in the monoadduct can be very beneficial as it can be easily reduced, eliminated, displaced, or converted into a Grignard reagent. The reaction mechanism has a conspicuous kinetic component and is governed by many steps and rates. For most optimized 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 describe 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 a new class of modified tris[2-(amino)ethyl]amine (TREN) based ligands that generated analogous copper complexes capable of slowing down the activation process to allow monitoring by UV/Vis spectroscopy.

Synthesis, characterization, and kinetic application of tris-(2-aminoethyl)amine (TREN) ligand derivatives

249th National Meeting (2015)

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