Mixed valence systems, electron transfer

A recently proposed semiclassical model, in which an electronic transmission coefficient and a nuclear tunneling factor are introduced as corrections to the classical activated-complex expression, is described. The nuclear tunneling corrections are shown to be important only at low temperatures or when the electron transfer is very exothermic. By contrast, corrections for nonadiabaticity may be significant for most outer-sphere reactions of metal complexes. The rate constants for the Fe(H20)6 +-Fe(H20)6 +> Ru(NH3)62+-Ru(NH3)63+ and Ru(bpy)32+-Ru(bpy)33+ electron exchange reactions predicted by the semiclassical model are in very good agreement with the observed values. The implications of the model for optically-induced electron transfer in mixed-valence systems are noted. 

A vibronic coupling model for mixed-valence systems has been developed over the last few years (1-5). The model, which is exactly soluble, has been used to calculate intervalence band contours (1, 3, 4, 5), electron transfer rates (4, 5, 6) and Raman spectra (5, 7, 8), and the relation of the model to earlier theoretical work has been discussed in detail (3-5). As formulated to date, the model is "one dimensional (or one-mode). That is, effectively only a single vibrational coordinate is used in discussing the complete ground vibronic manifold of the system. This is a severe limitation which, among other things, prevents an explicit treatment of solvent effects which are... 

Does T differ significantly from unity in typical electron transfer reactions It is difficult to get direct evidence for nuclear tunnelling from rate measurements except at very low temperatures in certain systems. Nuclear tunnelling is a consequence of the quantum nature of oscillators involved in the process. For the corresponding optical transfer, it is easy to see this property when one measures the temperature dependence of the intervalence band profile in a dynamically-trapped mixed-valence system. The second moment of the band,... 

Methods discussed so far for determination of x assume that two ions are present and that electron transfer can be observed —as, e.g., in a mixed-valence system. What can be obtained for systems (e.g., Fe(III)(H20) /Fe(II)(H O) ) where this is not... 

Dinuclear ruthenium complexes form the largest group by far of any mixed-valence system and are the exclusive subject of this chapter. Ruthenium is the transition metal of choice to study electron transfer or exchange because it is relatively inexpensive and forms stable Ru(III) and Ru(II) coordination complexes. In addition, the synthetic coordination chemistry of ruthenium is well developed (1). 

The intellectual push to study mixed-valence complexes was provided by the publication in 1967 of two review articles, by Allen and Hush (2) and Robin and Day (3), on the physical properties of mixed-valence systems. These were followed by Hush s publication (4) of his theoretical model of intervalence transitions, which provided a link between the properties of mixed-valence complexes in solution and the Marcus theory of intermolecular electron transfer (5, 6). The review by Robin and Day classified mixed-valence complexes into three types class I,... 

The simplest form of this expression obtains for degenerate electron transfer (AG ) in e.g. symmetrical mixed valence systems ... 

Rg. 13.14 A comparison of photochemical and thenwl eteciron-transfer processes in mixed valence systems. The photochemical pathway (top) allows electron transfer prior to bond-length adjustment, while the ihermal route (bottom) requires adjustment prior to electron transfer. (CreuU, C. Prog, inorg. Chem. W83,30. 1-73. Used with pemission.)... 

In three-dimensional mixed-valence systems, electron transfer can manifest itself as electrical conduction, thermally activated. Most work continues to focus on the better known semiconducting materials such as silicon-boron or silicon nitride " (at low temperature), or organic crystals of the anthracene type (at high temperature),or redox polymer-coated electrodes. In the last-mentioned case, the importance of ion migration as well as electron transfer has recently been emphasized. In the mixed-valent Tl(I)3Tl(III)Cl6, conductivity and isotopic exchange studies have been taken to indicate that cation transfer is the principal charge-carrying mechanism, and not electron transfer as such. " Mossbauer... 

Numerous other magnetic studies, especially of copper(ii) complexes, involve structures which resemble known mixed-valence systems or electron-transfer transition states. Examples include doubly bridged structures (3) and (4), single-atom bridges (CuOHCu), bridging by heterocyclic rings [Cu(imida-... 

The uv/vis/nir spectra of mixed-valence species exhibit unique low-energy intervalence charge transfer (IVCT) transitions which are absent in the fully reduced and oxidised complexes. Qass (valence localised) mixed-valence systems have broad, weak, structureless IVCT bands which are sensitive to molecular environment (eg solvent ). Detailed study of these bands in trapped valence species allows os to calculate intramolecular electron transfer rates. Class III (valence delocalised) systems have more intense low-energy transitions which are often structured and are largely insensitive to solvent. We will consider the degree of metal-metal interactions within class III species by analysis of low-energy absorption transitions. 

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