Abstract
The molecular structures of [CuII(dNbpy)2Br]+[CuIBr2]−, CuII(pmdeta)Br2, CuII(tNtpy)Br2, [CuII(hmteta)Br]+[Br]− and [CuII(cyclam)Br]+[Br]− [dNbpy=4,4′-di(5-nonyl)-2,2′-bipyridine, pmdeta=N,N,N′,N″,N″-pentamethyldiethylenetriamine, tNtpy=4,4′,4″-tris(5-nonyl)-2,2′:6′,2″-terpyridine, hmteta=1,1,4,7,10,10-hexamethyltriethylenetetramine, Me4cyclam=1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane] isolated from atom transfer radical polymerizations (ATRP) were determined. The CuII complexes showed either a trigonal bipyramidal structure as in the case of the dNbpy ligand, or a distorted square pyramidal coordination in the case of triamines and tetramines. Depending on the type of amine ligand, the complexes were either neutral (triamines) or ionic (bpy and tetramines). The counterions in the case of the ionic complexes were either bromide (Me4cyclam and hmteta) or the linear [CuIBr2]− anion (dNbpy). No direct correlation was found between the CuII–Br bond length and the deactivation rate constant in ATRP, which suggests that other parameters such as the entropy for the structural reorganization between the CuI and CuII complexes might play an important role in determining the overall activity of the catalyst in ATRP.
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