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Cyclic voltammetric studies of copper complexes catalyzing atom transfer radical polymerization
Author(s) -
Qiu Jian,
Matyjaszewski Krzysztof,
Thouin Laurent,
Amatore Christian
Publication year - 2000
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/1521-3935(20000901)201:14<1625::aid-macp1625>3.0.co;2-9
Subject(s) - chemistry , atom transfer radical polymerization , ligand (biochemistry) , bipyridine , redox , polymer chemistry , acetonitrile , amine gas treating , copper , cyclic voltammetry , catalysis , polymerization , electrochemistry , photochemistry , medicinal chemistry , inorganic chemistry , crystallography , organic chemistry , polymer , crystal structure , biochemistry , receptor , electrode
Several copper complexes used successfully as the catalysts for atom transfer radical polymerization (ATRP) were studied by cyclic voltammetry in acetonitrile. These complexes include CuBr or CuCl complexed by 2,2′‐bipyridine (bpy), 4,4′‐di(5‐nonyl)‐2,2′‐bipyridine (dNbpy), 4,4′‐di( n ‐nonyl)‐2,2′‐bipyridine (d n Nbpy), N,N,‐N ′, N ″, N ″‐pentamethyldiethylenetriamine (PMDETA), N,‐ N ‐bis(2‐pyridylmethyl)octylamine (BPMOA), N,N ‐bis(2‐pyridylmethyl)octadecylamine (BPMODA), tris[(2‐pyridyl)methyl]amine (TPMA) and tris[2‐(dimethylamino)ethyl]amine (Me 6 TREN), respectively. It was found that the E 1/2 value for the redox couple Cu I /Cu II strongly depends on the nature of the ligand and the halogen. As the number of coordination sites of the ligand increases, the reducing power of the corresponding Cu(I) complex also increases. With the same ligand, CuCl complexes usually have a lower redox potential than CuBr complexes. These general trends agree with the kinetic features of ATRP catalyzed by the corresponding complex, and a correlation between the redox potential and the apparent equilibrium constant of ATRP for methacrylate was observed. The possibility of using electrochemistry as a screening method for selecting ATRP catalysts is therefore further discussed.