Electrochemical Exploration of Active Cu-Based Atom Transfer Radical Polymerization Catalysis through Ligand Modification

Jamie N Melville; Paul V Bernhardt

doi:10.1021/acs.inorgchem.1c01001

Electrochemical Exploration of Active Cu-Based Atom Transfer Radical Polymerization Catalysis through Ligand Modification

Inorg Chem. 2021 Jul 5;60(13):9709-9719. doi: 10.1021/acs.inorgchem.1c01001. Epub 2021 Jun 18.

Authors

Jamie N Melville¹, Paul V Bernhardt¹

Affiliation

¹ School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane 4072, Australia.

PMID: 34142823
DOI: 10.1021/acs.inorgchem.1c01001

Abstract

The intersection between Cu-catalyzed atom transfer radical polymerization (ATRP) and organometallic mediated radical polymerization (OMRP) has been recently shown to be a result of competition between the Cu^I and Cu^II complexes of polyamine ligands for the same organic free radical. The tetradentate ligands N,N'-bis-2'-pyridylmethyl-ethane-1,2-diamine (L¹) and N,N'-dimethyl-N,N'-bis-2'-pyridylmethyl-ethane-1,2-diamine (L²) form stable Cu complexes which, depending on their oxidation state, can either liberate or complex organic radicals. Herein, we show that this process may be affected by subtle changes to the ligand system. Switching from a tertiary amine (L²) to a secondary amine (L¹) retains ATRP and OMRP activity through a series of cyclic voltammetry measurements in the presence of the initiator bromoacetonitrile.