Abstract

The oligomerization of [CuII(Hx(tmdnTAA))]x+ (x = 0, 1, 2 and (tmdnTAA))2- is 2,4,9,11-tetramethyl-dinaphto[14]-2,4,6,9,11,13-hexaeneN4) was initiated in homogeneous solution via the reaction of this Cu(II) complex with pulse radiolytically generated N3 {radical dot} radicals. The reaction produces Cu(III) intermediates which are rapidly converted to Cu(II) ligand-radical species. In contrast to the mechanism proposed for the electrochemical oligomerization, where the local concentration of radicals is probably high, the reaction kinetics in homogeneous solution is propagated by a process where the Cu(II) ligand-radical precursors react with [CuII(Hx(tmdnTAA))]x+. © 2008 Elsevier B.V. All rights reserved.