Molybdenum trivalent

Molybdenum(III) complexes include the molybdenum trihaUdes. Molybdenum trichoride [13478-18-7], trifluoride [20193-58-2], tribromide [13446-57-6], and ttiiodide [14055-75-5] are all known. The oxide dimolybdenum trioxide [1313-29-7], M02O2, and the seldom-studied sulfide analogue [12033-33-9], M02S2, are formally trivalent. 

Molecular examples of trivalent molybdenum are known in mononuclear, dinuclear, and tetranuclear complexes, as illustrated in Figure 5. The hexachloride ion, MoCk (Fig- 5a) is generated by the electrolysis of Mo(VI) in concentrated HCl. Hydrolysis of MoCP in acid gives the hexaaquamolybdenum(III) ion, Mo(H20) g, which is obtainable in solution of poorly coordinating acids, such as triflic acid (17). Several molybdenum(III) organometaUic compounds are known. These contain a single cyclopentadienyl ligand (Cp) attached to Mo (Fig. 5d) (27). 

Fe—Fe bond can be assigned structures 201 or 202 based on spectral data. The other product of this reaction is 193 (R = r-Bu), however, it is produced in minor amounts. Complexes 199 (R = R = r-Bu, R = Ph, R = r-Bu) were obtained. Reaction of 146 (M = Mo, R = Ph, R = R = Ft, R = r" = Me) with (benzyli-deneacetone)iron carbonyl gives rise to the bimetallic complex 200 (M = Mo), which reacts further with the free phosphole to form the bimetallic heteronuclear sandwich 203. The preferable coordination of the molybdenum atom to the dienic system of the second phosphole nucleus is rather unusual. The molybdenum atom is believed to have a greater tendency to coordinate via the trivalent phosphorus atom than via the dienic system. 

In the preparation of Mo/HUSY, the cluster 1 amounting to 2.5 wt% (as molybdenum metal) of HUSY was added to the suspension of HUSY 92% of the molybdenum was loaded onto HUSY. The Cl/Mo ratio of Mo/HUSY was found to be 0.34, suggesting that in ion exchange the cluster 1 acted as a trivalent cation on the average. These findings indicate that the protons in HUSY are less exchangeable by the cluster cation than the Na cations in NaY. 

Chemical precipitation is used in porcelain enameling to precipitate dissolved metals and phosphates. Chemical precipitation can be utilized to permit removal of metal ions such as iron, lead, tin, copper, zinc, cadmium, aluminum, mercury, manganese, cobalt, antimony, arsenic, beryllium, molybdenum, and trivalent chromium. Removal efficiency can approach 100% for the reduction of heavy metal ions. Porcelain enameling plants commonly use lime, caustic, and carbonate for chemical precipitation and pH adjustment. Coagulants used in the industry include alum, ferric chloride, ferric sulfate, and polymers.10-12... 

In addition to the successful reductive carbonylation systems utilizing the rhodium or palladium catalysts described above, a nonnoble metal system has been developed (27). When methyl acetate or dimethyl ether was treated with carbon monoxide and hydrogen in the presence of an iodide compound, a trivalent phosphorous or nitrogen promoter, and a nickel-molybdenum or nickel-tungsten catalyst, EDA was formed. The catalytst is generated in the reaction mixture by addition of appropriate metallic complexes, such as 5 1 combination of bis(triphenylphosphine)-nickel dicarbonyl to molybdenum carbonyl. These same catalyst systems have proven effective as a rhodium replacement in methyl acetate carbonylations (28). Though the rates of EDA formation are slower than with the noble metals, the major advantage is the relative inexpense of catalytic materials. Chemistry virtually identical to noble-metal catalysis probably occurs since reaction profiles are very similar by products include acetic anhydride, acetaldehyde, and methane, with ethanol in trace quantities. 

Surface analyses were investigated mainly by using XPS (Fig. 7). It was clearly indicated that many composite oxides found by XRD are located un-homogeneously in the catalyst particle. Molybdenum and bismuth are undoubtedly concentrated in the surface layer of the catalyst particle and divalent and trivalent metal cations are found in the bulk of the catalyst. As a result, it is clear that bismuth molybdates, especially its a-phase, is located on the surface of each particle, and metal molybdates of divalent and trivalent cations are situated in the bulk of the catalyst. 

Trivalent molybdenum is found in a few simple compounds. The black hydroxide, Mo(OH)3, dissolves in acids -with salt formation, yielding reddish-purple solutions which darken in colour. Upon evaporation crystalline salts are not obtained, but when the solution is taken to dryness a greyish-black residue remains, which can be redissolved in water to a dark grey solution. This may be accounted for by the readiness with which the salts undergo hydrolysis, with formation of the black hydroxide, possibly in the eoUoidal form. The similarity of molybdenum to chromium is seen in the series of complex For indications of basic properties in the trioxide, see p. 137. 

Other simple phosphates of trivalent raotybdenum have not been prepared, but the complex salt, sodium molybdenipyrophosphate, Na(MoP20,).12H.20, has been obtained as a brown crystalline precipitate by adding tripotassium molybdenum hexachloride, KgMoClg, to a solution of sodium pyrophosphate at 80° to 90° C. 

The molybdenum in these salts may be oxidised by ammoniaeal silver nitrate and the equivalent of the molybdenum calculated from the amount of silver liberated the results obtained indicate a trivalent molybdenum atom. 

In 1872 Mendeleeft pointed out that there was no place in the Periodic Table for a trivalent element of atomic weight 120, and drew attention to the similarity of uranium to chromium, molybdenum, and tungsten he therefore suggested that the atomic weight should be doubled, so that uranium could be placed below these elements in the table. He also formulated the oxides, by analog with those of the other elements in the group, as follows uranous oxide UOg, urano-... 

Volumetric methods for determining columbium are rapid and fairly satisfactory since tantajum does not interfere. But tungsten, molybdenum, and titanium must be completely removed. The methods depend on the reduction of pentavalent columbium to the trivalent condition by means of zinc, then the oxidation by standard permanganate. Taylor s method3 makes the reduction in a Jones reductor and the titration in an atmosphere of C02. Levy s method4 carries out the reduction and titration in an atmosphere of hydrogen in a conical flask from which the air is excluded. 

Trivalent uranium ion reduces water to hydrogen. Hence, stable aqueous solutions of trivalent uranium compounds cannot be prepared. Compounds of tetravalent uranium are generally similar to those of zirconium or thorium, except that some uranium compounds can be oxidized to the hexavalent form. Compounds of pentavalent uranium are of little importance because they disproportionate readily into tetravalent and hexavalent forms. The properties of hexavalent uranium are generally similar to those of hexavalent molybdenum or tungsten. In aqueous solution hexavalent uranium forms the uranyl ion UO2 ... 

From the above discussion it follows that tetravalent and hexavalent thorium, uranium, and plutonium can be separated from the trivalent rare-earth fission products by taking advantage of differences in complexing properties. More highly charged cation fission products, such as tetravalent cerium and the fifth-period transition elements zirconium, niobium, molybdenum, technetium, and ruthenium, complex more easily than the trivalent rare-earths and are more difficult to separate from uranium and plutonium by processes involving complex formation. 

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