Atom transfer radical addition (ATRA) catalyzed by copper complexes with N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) ligand

• Published in: Polymer (Guilford) Vol. 72; pp. 246 - 252
• Main Authors: Kaur, Aman, Gorse, Erin E., Ribelli, Thomas G., Jerman, Callista C., Pintauer, Tomislav
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 18.08.2015
• Subjects: Acetone; Ascorbic acid; Coordination compounds; Copper; Homogeneous catalysis; Ligands; Methyl alcohol; Solvents; Stereoselectivity; Tris(2-pyridyl)methyl amine; Copper; Tris(2-pyridyl)methyl amine; Homogeneous catalysis
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2015.02.021

Synthesis, characterization, electrochemical studies and ATRA activity of copper complexes with N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) ligand in the presence of ascorbic acid as a reducing agent were reported. [CuII(TPEN′)Br][Br] (TPEN′ denotes tetracoordinated ligand) catalyst showed a very low activity in ATRA of CBr4 to 1-octene, methyl methacrylate, methyl acrylate and styrene in methanol, which is a typical solvent used for ATRA reactions employing ascorbic acid. On the contrary, the yields and stereoselectivity towards monoadduct formation were dramatically increased in slightly polar but aprotic acetone. Based on molecular structures of isolated [CuII(TPEN)][BPh4] and [CuII(TPEN′)Br][Br] complexes, as well as UV–Vis and cyclic voltammetry studies, an equilibrium was proposed involving inactive [CuII(TPEN)]2+ and ATRP active [CuII(TPEN′)Br]+ cations The halidophilicity of the bromide-based deactivating complex ([CuII(TPEN′)Br][Br]) decreased approximately 750 times upon changing the solvent from acetone (KBr = 3000 ± 230) to methanol (KBr = 4.1 ± 0.1), explaining poor catalytic activity in methanol. In acetone, [CuII(TPEN′)Br][Br] complex was nearly as active in ATRA reactions employing ascorbic acid as previously reported [CuII(TPMA)Br][Br]. [Display omitted] •Copper complexes with TPEN ligand were successfully utilized in ATRA reactions in the presence of ascorbic acid.•The yields of the monoadduct were significantly increased in slightly polar but aprotic solvent such as acetone.•The halidophilicity of the Br-based deactivating complex decreased 750 times on changing solvent from acetone to methanol.•Relevant copper(II) species were successfully isolated and characterized in the solid state and solution.