Abstract
Novel mixed [Cu( 4a–c) 2]CF 3SO 3 pentanuclear copper(I)/chromium(0) complexes containing tweezer ligands that contain, within the same molecule, a 2,9-disubstituted-1,10-phenanthroline and two arene-chromium subunits. The mononuclear copper(I) complexes [Cu( 5a–c) 2] CF 3SO 3 have been prepared from the chromium free ligand species 5a–c, obtained by quantitative photochemical decomplexation of the parent species 4a–c. Cyclic voltammetry showed that in these complexes copper(I) can be reversibly oxidized to copper(II) in CH 2Cl 2. The Cu II/I couples are more positive in the presence of the four surrounding redox-active arenechromium subunits, revealing an electron-withdrawing effect. Complexes [Cu( 4c) 2] +, [Cu( 5c) 2] + form new species (1 : 1 ligand copper stoichiometry) upon addition of excess [Cu(CH 3CN) 4] +, which were identified electrochemically and by FAB + mass spectroscopy.
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