Redox active bridging ligands

An interesting redox-active bridging ligand that binds to one metal through two N-donor atoms and the other through two O-donor atoms is l,10-phenanthroline-5,6-diolate, (44).135... 

Redox-active bridging ligands do not always produce redox-active coordination networks. For example, redox-active azopyridines do not show any redox properties when they are incorporated into coordination networks. Toward the creation of new FCPs, we have been studying on the syntheses of redox-active coordination polymers. 

Bielawski et al. have developed Janus-head dicarbene ligands which are able to act as a bridge between two metal centers, thereby leading to dinuclear complexes of type 96 [58-60] (Fig. 32). More recently homonuclear bimetallic ruthenium(II) and iron(II) complexes 97 have been synthesized. It was hoped that the dicarbene ligand would interconnect the redox-active metal centers, but the... 

The hexanuclear Ru6 species has four outer and two inner metal centers oxidation active. Both in acetonitrile at room temperature ( 1/2 at + 1.52 V) and in liquid S02 at low temperature ( 1/2 at + 1.46 V), an oxidation process involving the practically simultaneous one-electron oxidation of the four outer Ru(II) centers is evidenced (Fig. 5.9 and Table 5.1). This confirms that the electronic interaction between metal centers that are not directly connected via a bridging ligand is negligible from an electrochemical viewpoint in the metal-polypyridine dendrimers. At more positive potentials, only recordable in liquid S02 at low temperature (Fig. 5.9), a bielectronic process, related to the simultaneous one-electron oxidation of the two inner metal centers at + 2.11 V, is found. This result was at a first sight surprising, since the redox... 

The thermodynamic stability of the binuclear site has been demonstrated by the spontaneous assembly of [Fe20(02CR)2L2] (13) from ferric salts in the presence of water, an alkyl carboxylate salt, and a tridentate nitrogen donor ligand L that can cap an octahedral face on iron (8). Suitable ligands include tris(pyrazolyl)borates and 1,4,7-triazacyclononanes. Structure (13) is in essence a portion of the basic ferric acetate structure. The complexes are excellent physical and structural models of the diiron sites and model some aspects of reactivity including redox activity and interconversion of the oxo and hydroxo bridge. 

The l,T-ferrocenediyl-bridged ligand system Fe[(C5H4) NPh]2 give access to redox-active chelate complexes of the type (83). ... 

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