Molybdenum anions

Molybdate orange and red are pigments (qv) that contain lead(II) molybdate [10190-33-3], PbMoO, formulated in mixed phases with PbCrO and PbSO. The mixed phase is more intensely colored than any of the component phases. Concerns about lead content are lessening the use of these materials (see also Paint). Various organic dyes are precipitated with heteropolymolybdates. This process allows the fixation of the dye in various fabrics. The molybdenum anion generally imparts light stabiHty to the colorant as weU (91). 

Molybdenum Anion exchange resin adsorption (Biorad Agl-X8), elution Graphite furnace AAS <10p,g/l... 

Molybdenum Anion-exchange on Dowex 1-X8 resin or Amberlite GC-40 Spectrophotometry [497-500,... 

Indeed the same color change occurs when the molybdenum anion and pyrylium cation are mixed in acetonitrile. However, the significantly diminished intensity of the orange color (and the reduced absorbance of the visible bands at = 508, 548 and 780 nm) indicates that lower concentrations of TPP- (by roughly a factor of 10) are formed in acetonitrile relative to dichloromethane containing the same salt concentrations. This observation, coupled with the lower concentrations of the 17-electron radical is ascribed to the equilibrium in Eq. (42), which is displaced toward the left in the more polar solvent (40). 

Most importantly, the new absorption band undergoes a progressive red (bathochromic) shift when the molybdenum anion is replaced by successively better anionic donors, such as those with tungsten (purple,... 

Highly selective reduction of aldehydes rather than ketones, even 4-f-butylcyclohexanone, has been achieved by a binuclear hydrido molybdenum anion (Et4N[ JL-HMo2(CO)io]) and acetic acid in refluxing THF," The stable complex is readily prepared from molybdenum hexacarbonyl, which can be recovered after reduction. The full value of this reagent in synthesis remains to be established. Tributyltin hydride has been shown to be effective for the selective reduction of aldehydes in the presence of dried silica gel which acts as a mild acid catalyst," The reaction proceeded at room temperature in cyclohexane, many common functional groups were inert under these conditions. 

The molybdenum anion in [piperazine][MoSJ has tetrahedral geometry. The Mo-S distances range from 2.168 to 2.199 A. 

Fig. 7. Representive stmctures for compounds of molybdenum(0) (a) Mo(CO)g (b) tris(acetonitrile)tris(carbonyl)molybdenum(0) (c) bis(l,2-diphenylphosphinoethane) bis (dinitrogen) molybdenum(0), [R2PCH2CH2PR2]2Mo(N2)2, where R = CgH, also known as Mo(dppe)2(N2)2, where dppe = 1,2 — diphenylphosphinoethane (d) cyclopentadienyl tricarbonyl molybdenum(0) anion, CpMo(CO)3, where Cp = cyclopentadienyl (e)...

Soil Nutrient. Molybdenum has been widely used to increase crop productivity in many soils woddwide (see Fertilizers). It is the heaviest element needed for plant productivity and stimulates both nitrogen fixation and nitrate reduction (51,52). The effects are particularly significant in leguminous crops, where symbiotic bacteria responsible for nitrogen fixation provide the principal nitrogen input to the plant. Molybdenum deficiency is usually more prominent in acidic soils, where Mo(VI) is less soluble and more easily reduced to insoluble, and hence unavailable, forms. Above pH 7, the soluble anionic, and hence available, molybdate ion is the principal species. 

Arsonium salts have found considerable use in analytical chemistry. One such use involves the extraction of a metal complex in aqueous solution with tetraphenyiarsonium chloride in an organic solvent. Titanium(IV) thiocyanate [35787-79-2] (157) and copper(II) thiocyanate [15192-76-4] (158) in hydrochloric acid solution have been extracted using tetraphenyiarsonium chloride in chloroform solution in this manner, and the Ti(IV) and Cu(II) thiocyanates deterrnined spectrophotometricaHy. Cobalt, palladium, tungsten, niobium, and molybdenum have been deterrnined in a similar manner. In addition to their use for the deterrnination of metals, anions such as perchlorate and perrhenate have been deterrnined as arsonium salts. Tetraphenyiarsonium permanganate is the only known insoluble salt of this anion. 

Selectivities to various isomers are more difficult to predict when metal oxides are used as catalysts. ZnO preferentially produced 79% 1-butene and several percent of i7j -2-butene [624-64-6] (75). CdO catalyst produced 55% 1-butene and 45% i7j -2-butene. It was also reported that while interconversion between 1-butene and i7j -2-butene was quite facile on CdO, cis—trans isomeri2ation was slow. This was attributed to the presence of a TT-aHyl anion intermediate (76). High i7j -2-butene selectivities were obtained with molybdenum carbonyl encapsulated in 2eohtes (77). On the other hand, deuteration using H1O2 catalyst produced predominantly the 1,4-addition product, trans-2-huX.en.e-d2 with no isotope scrambling (78). 

Metals that produce protective oxide layers (such as stainless steels) are especially susceptible to crevice attack. The reduced oxygen concentration in the crevice inhibits repair of the protective oxide film. This is especially true if acidic anions are present, which further retards oxide repair. Stainless steels containing molybdenum are usually less susceptible to attack. 

The reaetion of eone HCl and molybdenum aeetate at 0°C produees the diamagnetie red anion [Mo2Cl8]" (Fig. 23.11b) in whieh the 2 M0CI4 are in the eelipsed orientation relative to eaeh other and are held together solely by the Mo-Mo bond. At somewhat higher temperatures ( 50°C) the above reaetants also produee the [Mo2ClgH] ion whieh has the [Mj Clg] " strueture (Fig. 23.4) but with one of the bridging Cl atoms replaeed by a H atom. 

Molybdenum and tungsten hexacarbonyls are able to form anionic complexes (AsPli4)2[(OC)4M( -pz)2M(CO)4] upon reaction with sodium pyrazolate and PluAsCl (72CB3203). The cationic complexes [(rj -Cp)2Mo(/Lt-pz)2Mo(rj -Cp)2] " (n = 2, 3) are known as well (74HCA1988). The other representatives of the complexes containing an exobidentate ligand (26) are derived from 4//-pyrazoles [70ZAAC(379)169]. 

When methylene chloride was used as a solvent, it was found that 28 are obtained in minor amounts, while the dominating product is the -coordinated chloro-carbyne species [(> -Tp )Mo(CO)2(=CCl)], whose yield increases abruptly with substitution in the pyrazol-l-yl fragments (3-methyl-, 3,4,5-trimethyl-, and 3,5-dimethyl-4-chloro derivatives) [90AX(C)59,95JCS(D) 1709]. The tungsten analog can be prepared similarly. The chlorocarbyne molybdenum complex follows also from the reaction of the parent anion with triphenylsulfonium cation but conducted in dichloromethane. The bromo- and iodocarbyne derivatives are made similarly. 

The Fermentation Process The process by which this antifungal substance is produced is an aerobic fermentation of an aquaous nutrient medium inoculated with a pimaricin-producing strain of Streptomycesgihrosporeus. The nutrient medium contains an assimilable source of carbon such as starch, molasses, or glycerol, an assimilable source of nitrogen such as corn steep liquor and Inorganic cations such as potassium, sodium or calcium, and anions such as sulfate, phosphate or chloride. Trace elements such as boron, molybdenum or copper are supplied as needed in the form of impurities by the other constituents of the medium. 

A thin layer deposited between the electrode and the charge transport material can be used to modify the injection process. Some of these arc (relatively poor) conductors and should be viewed as electrode materials in their own right, for example the polymers polyaniline (PAni) [81-83] and polyethylenedioxythiophene (PEDT or PEDOT) [83, 841 heavily doped with anions to be intrinsically conducting. They have work functions of approximately 5.0 cV [75] and therefore are used as anode materials, typically on top of 1TO, which is present to provide lateral conductivity. Thin layers of transition metal oxide on ITO have also been shown [74J to have better injection properties than ITO itself. Again these materials (oxides of ruthenium, molybdenum or vanadium) have high work functions, but because of their low conductivity cannot be used alone as the electrode. 

Epoxidation systems based on molybdenum and tungsten catalysts have been extensively studied for more than 40 years. The typical catalysts - MoVI-oxo or WVI-oxo species - do, however, behave rather differently, depending on whether anionic or neutral complexes are employed. Whereas the anionic catalysts, especially the use of tungstates under phase-transfer conditions, are able to activate aqueous hydrogen peroxide efficiently for the formation of epoxides, neutral molybdenum or tungsten complexes do react with hydrogen peroxide, but better selectivities are often achieved with organic hydroperoxides (e.g., TBHP) as terminal oxidants [44, 45],... 

Stable enolates such as diethyl malonate anions react with allyl sulfones (or acetates) in the presence of nickel complexes to give a mixture of the a- and /-product83. The regioselectivity is generally poor in the nickel-catalyzed reaction, but the molybdenum-catalyzed reaction is selective for alkylation at the more substituted allylic site, thereby creating a quaternary carbon center84. 

The alkylation of allylic sulfides with stable anions takes place by using stoichiometric amounts of molybdenum hexacarbonyl86. Contrary to the catalytic reaction, the C —C bond formation occurs at the less hindered site of allyl groups in the stoichiometric reaction. 

---