p-Substituted Tris(2-pyridylmethyl)amines as Ligands for Highly Active ATRP Catalysts: Facile Synthesis and Characterization

Abstract

A facile and efficient two-step synthesis of p-substituted tris(2-pyridylmethyl)amine (TPMA) ligands to form Cu complexes with the highest activity to date in atom transfer radical polymerization (ATRP) is presented. In the divergent synthesis, p-Cl substituents in tris(4-chloro-2-pyridylmethyl)amine (TPMA^3Cl ) were replaced in one step and high yield by electron-donating cyclic amines (pyrrolidine (TPMA^PYR ), piperidine (TPMA^PIP ), and morpholine (TPMA^MOR )) by nucleophilic aromatic substitution. The [Cu^II (TPMA^NR2 )Br]⁺ complexes exhibited larger energy gaps between frontier molecular orbitals and >0.2 V more negative reduction potentials than [Cu^II (TPMA)Br]⁺ , indicating >3 orders of magnitude higher ATRP activity. [Cu^I (TPMA^PYR )]⁺ exhibited the highest reported activity for Br-capped acrylate chain ends in DMF, and moderate activity toward C-F bonds at room temperature. ATRP of n-butyl acrylate using only 10-25 part per million loadings of [Cu^II (TPMA^NR2 )Br]⁺ exhibited excellent control.

Keywords: ATRP; amine ligands; catalysis; copper; polymer synthesis.