Bridged electron transfer intermediates

Three oxidations states are potentially available in a binuclear iron center. Enzymes with octahedral fi-o o bridged iron clusters can be isolated in each of the three states the diferric and diferrous states appear to be the functional terminal oxidation states for most of the enzymes, while the mixed valence state may be an important intermediate or transition state for some reactions (Que and True, 1991). In these enzymes the cluster participates primarily as a two-electron partner in the redox of substrates, perhaps using sequential one-electron steps. Without additional coupled redox steps the enzyme is in a new oxidation state after one turnover. In contrast only the diferric and mixed valence oxidation states have been found for 2Fe 2S clusters. The diferrous state may not be obtainable because of the high negative charge on [2Fe 2S(4RS)] versus -1 or 0 net charge for the diferrous octahedral (i.e., non-Fe S) clusters. The 2Fe 2S proteins either are one-electron donor/acceptors or serve as transient electron transfer intermediates. 

Fig. 11. Top molecular orbital energies for precursor, structure C (broken lines) and for bridged intermediate, structure D (full lines). Bottom bridging energy (AE) for N =0 (full line) and N = 1 (broken line), where N is the number of electrons transferred from the carbon residue to the platinum. The energies are plotted as functions of the 7rC3-to-platinum overlap integral (S). The energy unit 0 [ is the absolute value of the exchange integral between a pair of p1 orbitals in benzene. For structures C and D, cf. reaction (7). After J. R. Anderson and N. R. Avery, J. Calal. 7, 315 (1967).

Figure 4. Schematic of electron transfer processes for 2,6-disubstituted phenol. The ligand groups are indicated as Am and the intermediate polymer chain segments as straight lines, (a) Hydroxo-bridged catalyst (b) chloro-bridged catalyst.

Inner-sphere electron transfers involve the inner coordination sphere of the metal complexes and usually take place through a bridging ligand. The classic example, typical of those studied and explained by H. Taube, is illustrated by Figure 1.11 s reaction sequence adapted from reference 7. In this reaction sequence, production of [Cr(III)(Fl20)5Cl] " implies that electron transfer through the bridged intermediate from Cr(II) to Co(III) and CF transfer from Co to Cr are mutually interdependent acts. 

The high lability of bound N2 in [FeII(CN)5N2]3 regenerates the active site, namely the [FeII(CN)5H20]3 ion, which is able to further bind and process hydrazine. A more detailed kinetic study could be warranted for this interesting set of reactions. Some uncertainties still remain as to the nature of the intramolecular electron-transfer rate processes (91). At the employed concentration levels of the complex, the participation of mixtures of mononuclear and dinuclear complexes complicate the spectral evolution. Even the nature of the dinuclear intermediates (cyano- or hydrazino-bridged) could be put into question (probably both are involved, due to the labile interconversion equilibria). The participation of Fe(III) species, either in the mononuclear or dinuclear species, as reactive intermediate precursors of the formation of diazene and N2... 

Mixed-valence species containing V11 and Viv bridged by an oxygen atom were intermediate in electron transfer between [V(Hedta)]- and [VO(Hedta)], and [V(edta)]2 and [VO(edta)]2-.815 Similarly bridged species were assumed in the reaction of [V(H20)6]2+ with [V0(H20)5]2+. Vanadium(III) dimeric complexes are the reaction products (see Section 33.4.9.3). 

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