Abstract
The copper complexes [Cu3(O2CMe)5{P(OR)3}2](1; R = Me or Et), [Cu(O2CMe){P(OR)3}(bpy)](2; R = Me or Et)(bpy is 2,2′-bipyridine), and [Cu(O2CMe){P(OEt)3}2] react with certain 2-halogenoazobenzene compounds, ArX, at room temperature to form the corresponding dialkyl arylphosphonates, ArP(O)(OR)2, and the products, ArH and Ar2, of reductive substitution and biaryl coupling. The ester, MeCO2R, and a copper(I) halide complex (e.g. [CuX{P(OR)3}]) are also formed. Kinetic studies of the reactions of some of these copper complexes with 2′-acetamido-6-bromo-4′-diethylamino-2,4-dinitroazobenzene in alcohol solution show that the phosphonation reactions are equal concentration second-order processes in each case. The effects of a radical scavenger and of light on the reaction suggest the involvement of radicals in the formation of ArH and Ar2, but not in the formation of ArP(O)(OR)2. The effects of different substituents in ArX, of changes in solvent, and of various additives on these reactions are investigated. A mechanism involving concerted nucleophilic substitution within the coordination sphere of copper(I) is proposed.
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