Molybdenum valency

D. Quantitative Studies on the Rapid Signal and Molybdenum Valency... 

Fig. 2. X-ray absorption near-edge structure (XANES) of reference compounds with various molybdenum valence states and mine tailings samples. The Mo K-edge excitation potential for molybdenum in the ground state (Mo°) is at 20000 eV. The Mo K-edge excitation potential increases with increasing valence state. 

In this paper factors controlling the catalytic activity in the hydrodesulfurization reaction (HDS) are discussed. The SiOa-supported phosphormolybdenum heteropolyacid (HPMo) is used as a model catalyst. Two types of the catalyst deactivation have been shown. The reversible deactivation effect is related with changes in the molybdenum valence, its 0- and 0,S-surrounding and adsorbtion of the S-containing reaction products. The HDS activity is irreversibly changed when the transformation of the catalyst phase composition is carried out ... 

Physical Properties. Molybdenum has many unique properties, leading to its importance as a refractory metal (see Refractories). Molybdenum, atomic no. 42, is in Group 6 (VIB) of the Periodic Table between chromium and tungsten vertically and niobium and technetium horizontally. It has a silvery gray appearance. The most stable valence states are +6, +4, and 0 lower, less stable valence states are +5, +3, and +2. 

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). 

Fig. 1.—Values of the metallic radius for ligancy 12, represented by circles, for the elements yttrium to silver. The straight line represents the expected values for valence of other metals equal to the valence of molybdenum that is, it shows the effect of increasing nuclear charge only.

The approximate correctness of the relative values of fav given in the table is supported by the observed values of the metallic radii. Values of R for ligancy 12 are shown in Figure 1, with a straight line with slope that represents the change in radius with atomic number for constant valence and type of orbital, as given in Figure 3 of an earlier paper.17 The points lie above the line by amounts that indicate a monotonic decrease in valence to both sides of molybdenum. 

Complexes of molybdenum in the lower valence-states of -t 2 and + 3 have been produced only in the past two years. For the Mo(II) species, the usual starting-material is Mo2(acetate>4. Reaction of this with KS2COEt in THF gives two products, a green complex tentatively assigned as [Mo2(Etxant>4], which solvates to form the red complex [Mo2(Etxant)4(THF)2]. The structure of the latter complex was elucidated by X-ray analysis 169). Steele and Stephenson 170) were also able to synthesize a red, crystalline solid (methanol solution), which they formulated as [Mo(Etxant)2]2 (XI), and reacted this with Lewis bases, e.g., pyridine, to form [Mo(Etxant)2L]2- Thus, there appears to be a difference between the two compounds formulated as [Mo2(Et-xant)2]2 that... 

Solid-state cluster chemistry is dominated by octahedral (M 5L8)L6 and (MsLi2)L units which are the focus of this paper. These two cluster types are different in the way the metal octahedral core is surrounded by the ligands. In (MsLg)L6-type clusters (Fig. 6.1a), typical for molybdenum and rhenium halides, chalcogenides, and chalcohalides, eight innei hgands (L ) cap the octahedron faces and six outer ligands (L ) are located in the apical positions [9]. For metals with a smaller number of valence electrons, the (M6L i2)L -type clusters... 

The cations in transition metal oxides often occur in more than one oxidation state. Molybdenum oxide is a good example, as the Mo cation may be in the 6-r, 5-r, and 4+ oxidation states. Oxide surfaces with the cation in the lower oxidation state are usually more reactive than those in the highest oxidation state. Such ions can engage in reactions that involve changes in valence state. 

The enzymes are protein molecules having globular structure, as a rule. The molecular masses of the different enzymes have values between ten thousands and hundred thousands. The enzyme s active site, which, as a rule, consists of a nonproteinic organic compound containing metal ions of variable valency (iron, copper, molybdenum, etc.) is linked to the protein globule by covalent or hydrogen bonds. The catalytic action of the enzymes is due to electron transfer from these ions to the substrate. The protein part of the enzyme secures a suitable disposition of the substrate relative to the active site and is responsible for the high selectivity of catalytic action. 

The situation is very similar in the Chevrel phases. These are ternary molybdenum chalcogenides A,.[Mo6Xg] (A = metal, X = S, Se) that have attracted much attention because of their physical properties, especially as superconductors. The parent compound is PbMo6Sg it contains Mo6Sg clusters that are linked with each other in such a way that the free coordination sites of one cluster are occupied by sulfur atoms of adjacent clusters (Fig. 13.9). The electric properties of Chevrel phases depend on the number of valence electrons. With 24 electrons per cluster (one electron pair for each edge of the... 

The catalyst is preliminarily oxidized to the state of the highest valence (vanadium to V5+ molybdenum to Mo6+). Only the complex of hydroperoxide with the metal in its highest valence state is catalytically active. Alcohol formed upon epoxidation is complexed with the catalyst. As a result, competitive inhibition appears, and the effective reaction rate constant, i.e., v/[olefin][ROOH], decreases in the course of the process due to the accumulation of alcohol. Water, which acts by the same mechanism, is still more efficient inhibitor. Several hypothetical variants were proposed for the detailed mechanism of epoxidation. 

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