Mixed valence compounds oxides

Diffraction Methods in Inorgaitic Chemistry Electronic Structure of Solids Mixed Valence Compounds Oxides Solid-state Chemistry Solids Computer Modeling. 

The reduction of molybdate salts in acidic solutions leads to the formation of the molybdenum blues (9). Reductants include dithionite, staimous ion, hydrazine, and ascorbate. The molybdenum blues are mixed-valence compounds where the blue color presumably arises from the intervalence Mo(V) — Mo(VI) electronic transition. These can be viewed as intermediate members of the class of mixed oxy hydroxides the end members of which are Mo(VI)02 and Mo(V)0(OH)2 [27845-91-6]. MoO and Mo(VI) solutions have been used as effective detectors of reductants because formation of the blue color can be monitored spectrophotometrically. The nonprotonic oxides of average oxidation state between V and VI are the molybdenum bronzes, known for their metallic luster and used in the formulation of bronze paints (see Paint). 

Oxide materials in the colored state are usually mixed-valence compounds with a variable range of composition. The color usually arises from low-energy intraband electronic transitions. 

The localized-valence halogen-bridged platinum(II)/platinum(IV) complexes (175) are of interest because of their highly anisotropic electrical and optical properties. The complexes are characterized by broad and intense intervalence bands in their electronic spectra.542 Partial oxidation of [PtCl(dien)]Cl with iodine yields the mixed valence species [PtI(dien)][PtI3(dien)]I2,543 but when 4Me-dien is used, the mixed valence compound is only obtained if it is trapped quickly, before isomerization of the meridional platinum(IV) complex to a facial form.544 Although these species nominally have localized valences, the extent of delocalization increases as the bridging halide... 

For the purpose of this discussion, a mixed valence compound is defined as a compound containing two or more metal atoms with an average oxidation state which is either... 

X-Ray photoelectric ionization is believed to take place in a time interval of about 10-18 s. Therefore separate XPS peaks are possible for atoms if the lifetime of the asymmetric electronic state is greater than about 10 18 s, whether or not the atoms are structurally equivalent. We may represent the ground state of a localized mixed valence compound (involving two metal atoms differing in oxidation state by one unit) by the following formula, where the dot represents the extra valence electron M—M. The two possible XPS transitions can then be represented as follows, where the asterisk indicates core ionization,... 

Optical charge transfer (CT) is commonly observed in un-symmetrical molecules or molecular complexes in which there are sites of distinctly different ionization energies and electron affinities. The origin and properties of optical charge transfer transitions provide the basis for this account. A convenient place to begin chemically is with mixed-valence compounds and two examples are shown below (1-3). In the first (eq 1), the sites of different oxidation states are held in close... 

This has the very important consequence, as we show in more detail later, that no totally symmetric mode of a mixed-valence compound can contribute to the intervalence bandwidth (in the approximation of equal force constants in both oxidation states). For the moment we therefore drop the terms in Q+ and define the dimensionless variables... 

Direct Synthesis reaction of, 6 395 fluoride, 21 235, 237, 239, 249 homopolyatomic cations, 17 82 ion, stereochemistry, 2 40-41, 44-45 isocyanates, preparation, 9 158 properties, 9 157 isothiocyanates, properties, 9 177 mixed valence compounds of, 10 375-381 crystal structure of, 10 376 diffuse reflectance spectrum of, 10 380 structure of Pb," ion, 10 381 nuclear magnetic shielding, 22 224 organometallic compounds, 2 82, 88, 89 oxide, neutron diffraction studies on, 8 231-233... 

The salt may be best described as a mixed-valence compound containing platinum in the 2.3+ oxidation state. The combination of the mixed-valence state, the very short Pt— Pt separation of 2.89 A (only approximately 0.1 A longer than in platinum metal), and the formation of linear Pt—Pt chains along the c axis gives rise to the high, anisotropic metallic conductivity in this material.1... 

Although there are many features common to synthetic oxides and minerals, fundamental studies of the charge-transfer processes in mixed-valence compounds can only be systematically carried out on synthetic oxides of controlled stoichiometry and impurity concentration. However, with the exception of Seebeck coefficients, transport measurements require single-crystal data if quantitative interpretations are to be made. Nevertheless, conductivity data for polycrystalline samples of cubic phases are useful if the samples are dense and care has been taken to eliminate any segregation of impurities into the grain boundaries. 

Nonstoichiometric compounds are mixed-valence compounds with nonintegral electron/atom ratios. Electronic properties of these compounds depend crucially on the nature and magnitude of nonstoichiometry. Electronic conduction in many such compounds occurs by hopping between the cations of different valencies (e.g. Pr " " and Pr" " in Pri2022)- Nonstoichiometry with a wide range of compositions is more common in oxides, sulphides, and related materials where the bonding is not completely ionic. In ionic nonstoichiometric compounds, structural rearrangements... 

In spite of the abundant work on synthetic, thermodynamic, structural, and spectroscopic aspects of mixed-valence compounds, the dynamic solution behavior toward external redox reagents has not been much addressed. When such compounds are unsymmetrical and valence-localized, several problems arise when a fully reduced dinuclear complex reacts with an oxidant. Haim pioneered a systematic study performed with different systems reacting with a common two-electron oxidant, peroxydisulfate (126). A relevant example is given by reaction (35) ... 

The oxidation of 8 resulted in the mixed-valence compound 9 [38] which contain the same cation as the complexes 5 and 7 described above and an AumCI4 anion. The main interesting feature is the one-dimensional chain arrangement in the crystal, with alternating cations and anion separated by intermetallic distances of 3.404(2) A (Au -Au111) and 4.658 A (Hgn-Auln) (Figure 4.5). 

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