Atom Transfer Radical Polymerization (ATRP) is one of the most efficient controlled radical polymerization techniques used for the preparation of various polymers with well defined features such as high molecular weights, low polydispersities and precise molecular architectures [1]. The process is catalyzed by transition metal complexes, especially copper(I) complexes with nitrogen-based ligands [2]. Factors that affect the equilibrium between the activation step in which the propagating radicals are generated and the deactivation step in which the latter are converted to dormant species include disproportionation of the metal complex, standard potentials of the catalyst and dormant species and halogenophilicity of the metal complex [3]. In this communication, we report the results of a thermodynamic study of copper complexes with pentamethyl-diethylenetriamine and tris[2-(dimethylamino)ethyl]amine in acetonitrile. In particular, we determined the stability constants of Cu(II) and Cu(I) complexes as well as the standard potentials of the Cu(II)/Cu(I) and Cu(I)/Cu couples. 1. Braunecker, W.A.; Matyjaszewski, K. Prog. Polym. Sci. 2007, 32, 93-146. 2. Pintauer, T.; Matyjaszewski, K. Coord. Chem. Rev. 2005, 249, 1155-1184. 3. Tsarevsky, N.V; Braunecker, W.A; Matyjaszewski, K. J. Organomet. Chem. 2007, 3212-3222.

Thermodynamic properties of copper complexes used as catalysts in Atom Transfer Radical Polymerization

GENNARO, ARMANDO;AHMED ISSE, ABDIRISAK;DI MARCO, VALERIO
2009

Abstract

Atom Transfer Radical Polymerization (ATRP) is one of the most efficient controlled radical polymerization techniques used for the preparation of various polymers with well defined features such as high molecular weights, low polydispersities and precise molecular architectures [1]. The process is catalyzed by transition metal complexes, especially copper(I) complexes with nitrogen-based ligands [2]. Factors that affect the equilibrium between the activation step in which the propagating radicals are generated and the deactivation step in which the latter are converted to dormant species include disproportionation of the metal complex, standard potentials of the catalyst and dormant species and halogenophilicity of the metal complex [3]. In this communication, we report the results of a thermodynamic study of copper complexes with pentamethyl-diethylenetriamine and tris[2-(dimethylamino)ethyl]amine in acetonitrile. In particular, we determined the stability constants of Cu(II) and Cu(I) complexes as well as the standard potentials of the Cu(II)/Cu(I) and Cu(I)/Cu couples. 1. Braunecker, W.A.; Matyjaszewski, K. Prog. Polym. Sci. 2007, 32, 93-146. 2. Pintauer, T.; Matyjaszewski, K. Coord. Chem. Rev. 2005, 249, 1155-1184. 3. Tsarevsky, N.V; Braunecker, W.A; Matyjaszewski, K. J. Organomet. Chem. 2007, 3212-3222.
2009
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/2482892
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