A radical-bridged bis(ferrocenylcopper(I)) complex: Structural identity, multifrequency EPR, and spectroelectrochemistry

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Inorganica Chimica Acta, 361 (6): 1699--1704 (2008)
DOI: 10.1016/j.ica.2007.02.006


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)



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