p‐Substituted Tris(2‐pyridylmethyl)amines as Ligands for Highly Active ATRP Catalysts: Facile Synthesis and Characterization
- 16 May 2020
- journal article
- research article
- Published by Wiley in Angewandte Chemie
- Vol. 59 (35), 14910-14920
- https://doi.org/10.1002/anie.202004724
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 (TPMA3Cl) were replaced in one step and high yield by electron-donating cyclic amines (pyrrolidine (TPMAPYR), piperidine (TPMAPIP), and morpholine (TPMAMOR)) by nucleophilic aromatic substitution. The [CuII(TPMANR2)Br]+ complexes exhibited larger energy gaps between frontier molecular orbitals and >0.2 V more negative reduction potentials than [CuII(TPMA)Br]+, indicating >3 orders of magnitude higher ATRP activity. [CuI(TPMAPYR)]+ 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 [CuII(TPMANR2)Br]+ exhibited excellent control.Funding Information
- Division of Chemistry (CHE 1707490, CHE 2000391)
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