Amines inner-sphere electron transfer

Dooley et al. first proposed an inner-sphere electron transfer mechanism where O2 binds directly to copper(I) 55 this was based upon precedence that suggested very rapid reactions between O2 and synthetic copper(I) compounds used as spectroscopic models for enzyme active sites. A three-coordinate copper(I) geometry in the CAOs had been demonstrated upon reduction with dithionite under anaerobic conditions.56 The reduction of the enzyme anaerobically with primary amine substrates actually produces two states, a copper(I)/semiquinone and a copper (II)/aminoquinol (Figure 9.11). In plant-derived and bacterial CAOs, these states have been demonstrated to exist in rapid equilibrium, due to intraprotein electron... 

There are also several nonaqueous redox systems which proceed by either outer- or inner-sphere electron transfer (OSET or ISET). As already stated before, aromatic amines accelerate decomposition of peroxides by electron transfer and formation of peroxide radical anions as depicted in equation 19 ... 

Photolysis " of the ion pair (NH3)RuCf -Ru(CN)r leads to reduction of the amine complex which rapidly hydrolyzes. A further inner-sphere electron transfer gives the bridged product [(NH3)5Ru(III)NCRu(II)-(CN)5]. 

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