Macrocyclic Copper(II) Complexes as Catalysts for Electrochemically Mediated Atom Transfer.
Inorg Chem
; 63(14): 6453-6464, 2024 Apr 08.
Article
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| MEDLINE
| ID: mdl-38526552
ABSTRACT
Copper-catalyzed electrochemical atom transfer radical addition (eATRA) is a new method for the creation of new C-C bonds under mild conditions. In this work, we have explored the reactivity of an analogous series of N4 macrocyclic CuII complexes as eATRA precatalysts, which are primed by reduction to their monovalent oxidation state. These complexes were fully characterized structurally, spectroscopically, and electrochemically. A spectrum of radical activation reactivity was found across the series [CuI(Me4cyclen)(NCMe)]+ (Me4cyclen = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane), [CuI(Me4cyclam)(NCMe)]+ (Me4cyclam = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), and [CuI(Me2py2clen)(NCMe)]+ (Me2py2clen = 3,7-dimethyl-3,7-diaza-1,5(2,6)-dipyridinacyclo-octaphane). The rate of radical production by [Cu(Me2py2clen)(NCMe)]+ was modest, but rapid radical capture to form the organocopper complex [CuI(Me2py2clen)(CH2CN)] led to a dramatic acceleration in catalysis, greater than seen in any comparable Cu complex, but this led to rapid radical self-termination instead of radical addition.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Año:
2024
Tipo del documento:
Article
País de afiliación:
Australia