Synthesis and Characterization of the Most Active Copper ATRP Catalyst Based on Tris[(4-dimethylaminopyridyl)methyl]amine

2018 
The tris[(4-dimethylaminopyridyl)methyl]amine (TPMANMe2) as a ligand for copper-catalyzed atom transfer radical polymerization (ATRP) is reported. In solution, the [CuI(TPMANMe2)Br] complex shows fluxionality by variable-temperature NMR, indicating rapid ligand exchange. In the solid state, the [CuII(TPMANMe2)Br][Br] complex exhibits a slightly distorted trigonal bipyramidal geometry (τ = 0.89). The UV–vis spectrum of [CuII(TPMANMe2)Br]+ salts is similar to those of other pyridine-based ATRP catalysts. Electrochemical studies of [Cu(TPMANMe2)]2+ and [Cu(TPMANMe2)Br]+ showed highly negative redox potentials (E1/2 = −302 and −554 mV vs SCE, respectively), suggesting unprecedented ATRP catalytic activity. Cyclic voltammetry (CV) in the presence of methyl 2-bromopropionate (MBrP; acrylate mimic) was used to determine activation rate constant ka = 1.1 × 106 M–1 s–1, confirming the extremely high catalyst reactivity. In the presence of the more active ethyl α-bromoisobutyrate (EBiB; methacrylate mimic), total c...
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