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Synthesis 2017; 49(15): 3311-3322
DOI: 10.1055/s-0036-1588873
short review
© Georg Thieme Verlag Stuttgart · New York

Electron Transfer Reactions in Atom Transfer Radical Polymerization

Autor*innen

  • Marco Fantin  *

    a   Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA   eMail: mfantin@andrew.cmu.edu   eMail: km3b@andrew.cmu.edu

  • Francesca Lorandi

    b   Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy

  • Armando Gennaro

    b   Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy

  • Abdirisak A. Isse

    b   Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy

  • Krzysztof Matyjaszewski*

    a   Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA   eMail: mfantin@andrew.cmu.edu   eMail: km3b@andrew.cmu.edu

K.M. acknowledges support from NSF (CHE 1400052).
Weitere Informationen

Publikationsverlauf

Received: 12. Mai 2017

Accepted: 15. Mai 2017

Publikationsdatum:
04. Juli 2017 (online)

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Graphical Abstract

This paper is dedicated to the 70th birthday of Professor Herbert Mayr, who pioneered kinetic and thermodynamic measurements of reactions between electrophiles and nucleophiles that were extremely helpful for understanding carbocationic polymerization and also inspired the authors’ approach to atom transfer radical polymerization, especially eATRP.

Abstract

Electrochemistry may seem an outsider to the field of polymer science and controlled radical polymerization. Nevertheless, several electrochemical methods have been used to determine the mechanism of atom transfer radical polymerization (ATRP), using both a thermodynamic and a kinetic approach. Indeed, electron transfer reactions involving the metal catalyst, initiator/dormant species, and propagating radicals play a crucial role in ATRP. In this mini-review, electrochemical properties of ATRP catalysts and initiators are discussed, together with the mechanism of the atom and electron transfer in ATRP.

1 Introduction

2 Thermodynamic and Electrochemical Properties of ATRP Catalysts

3 Thermodynamic and Electrochemical Properties of Alkyl Halides and Alkyl Radicals

4 Atom Transfer from an Electrochemical and Thermodynamic Standpoint

5 Mechanism of Electron Transfer in ATRP

6 Electroanalytical Techniques for the Kinetics of ATRP Activation

7 Electrochemically Mediated ATRP

8 Conclusions

Key words

atom transfer reactions - electrochemical properties - metal catalyzed atom abstraction - alkyl halides - alkyl radicals - eATRP - ATRA