Département de chimie moléculaire

The paramagnetic blue complex {\{}($μ$-adcOtBu)[Cu(dppf)]2{\}}(PF6) contains two heterodinuclear 1,1'-bis(diphenylphosphinoferrocene)copper(I) moieties, bridged by the radical anion of di-tert-butylazodicarboxylic ester (adcOtBu). The assignment of oxidn. states is supported by crystal structure detn. and by variable frequency EPR spectroscopy which provides hyperfine (9.5 GHz) and g anisotropy information (285 GHz). Cyclic voltammetry and UV/visible/NIR spectroelectrochem. indicate reversible 1-electron oxidn. of the adcOtBu·- bridge prior to the quasi-reversible two-electron oxidn. of the well sepd. (12.55 {\AA}) ferrocene termini. One-electron redn. to the adcOtBu2- bridged system occurs with concomitant loss of the long-wavelength metal-to-ligand charge transfer absorption. [on SciFinder(R)]