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Copper Catalysed Atom Transfer – New Applications in Electrosynthesis

Abstract

Cu complexes of polyamine ligands have emerged as the catalysts of choice in controlled reversible (‘living’) polymerization reactions including atom transfer radical polymerization (ATRP).^[1,2] The role of the Cu complex is to convert an alkyl halide (RBr) into an organic radical via a coupled electron and atom transfer radical activation reaction (see Scheme, right). We have investigated these reactions using spectroscopic and electrochemical methods and have found that accurate rate constants for these chemical reactions coupled triggered by redox reactions at the Cu complex can be determined by simulation of the experimental cyclic voltammetry data.^[3-6]

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In more recent work we have discovered that rare organocopper(II) complexes (highlighted in the left of the Scheme) can be prepared in an electrochemical synthesis^[7-8] and used as catalysts in controlled electrochemical atom transfer radical addition (eATRA) reactions. This has opened new opportunities in organic electrosynthesis. This methodology will be presented and new directions we are investigating will be discussed.

References

[1]           Matyjaszewski, K.; Xia, J. Chem. Rev. 2001, 101, 2921-2990.

[2]           Magenau, A.J.D.; Strandwitz, N.C.; Gennaro, A.; Matyjaszewski, K. Science 2011, 332, 81-84.

[3]           Bell, C.A.; Bernhardt, P.V.; Monteiro, M.J. J. Am. Chem. Soc.  2011, 133, 11944–11947.

[4]           Zerk, T.J.; Bernhardt, P.V. Dalton Trans. 2013, 42, 11683-11694.

[5]           Zerk, T.J.; Bernhardt, P.V. Inorg. Chem. 2014, 53, 11351-11353

[6]           Zerk, T.J.; Bernhardt, P.V. Inorg. Chem. 2017, 56, 5784-92.

[7]           Gonzálvez, M.A.; Harmer, J.R.; Bernhardt, P.V. Inorg. Chem. 2021, 60, 10648-10655.

[8]           Gonzálvez, M.A.; Su, C.; Williams, C.M.; Bernhardt, P.V. Chem. Sci. 2022, 13, 10506-10511.