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Issue 6, 2007
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Enhanced kinetic inertness in the electrochemical interconversion of Cu(i) double helical to Cu(ii) monomeric complexes

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Abstract

Three new ligands made of two iminoquinoline halves separated by an (R,R)-trans-1,2-cyclohexenediyl spacer have been synthesized. These ligands feature –OR functions appended in the 8-positions of the quinoline rings (R = n-alkyl). The ligands display a behaviour similar to that of their analogues that contain unsubstituted quinolines, forming a bistable system with copper. [Cu2L2]2+ helicates are obtained with Cu+ and [CuL]2+ monomers with Cu2+, as shown by UV/Vis titrations, determination of complex formation constants, mass and NMR measurements, and X-ray crystallographic analysis. The OR groups are found to be non-coordinating, but the presence of such substituents on the quinoline rings slows the electrochemical interconversion of [Cu2L2]2+ into [CuL]2+. In particular, oxidation of [Cu2L2]2+ gives a reversible two-step profile in cyclic voltammetry experiments, due to the formation of the Cu2+ helicate [Cu2L2]4+, that does not evolve into [CuL]2+in the CV experiment time scale.

Graphical abstract: Enhanced kinetic inertness in the electrochemical interconversion of Cu(i) double helical to Cu(ii) monomeric complexes

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Publication details

The article was received on 12 Jan 2007, accepted on 21 Mar 2007 and first published on 03 Apr 2007


Article type: Paper
DOI: 10.1039/B700488E
New J. Chem., 2007,31, 927-935

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    Enhanced kinetic inertness in the electrochemical interconversion of Cu(I) double helical to Cu(II) monomeric complexes

    P. Pallavicini, M. Boiocchi, G. Dacarro and C. Mangano, New J. Chem., 2007, 31, 927
    DOI: 10.1039/B700488E

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