Abstract
Alkyl radicals are efficiently oxidized by a variety of copper(II) complexes at rates with second order rate constants in excess of 106 M-1 sec-1. The oxidation of alkyl radicals to alkyl halides (chloride, bromide and iodide) and pseudohalides (thiocyanate, azide and cyanide) by copper(II) halides and pseudohalides, respectively, is described as a ligand transfer process. Copper(II) acetate, Perchlorate and triflate, on the other hand, oxidize alkyl radicals by an electron transfer process to alkenes (oxidative elimination) and alkyl derivatives from the solvent (oxidative substitution). The mechanism of electron transfer and ligand transfer oxidation by various copper(II) complexes is studied in detail. Solvolytic routes can be described in which carbonium ion intermediates are formed from metastable alkylcopper species. Atom transfer of the ligand to the alkyl radical represents an alternative route for the oxidation to proceed without the intervention of ionic intermediates. The ligand associated with the copper(II) nucleus and the solvent play critical roles in determining the relative importance of the various pathways for oxidation.
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