The Molybdate Complexes

Turning from the first to the second transition metal series it should be realized that the strength of spin-orbit coupling increases. This is of importance, since we are dealing in luminescence with spin-forbidden transitions. Although this effect is discernable already in the second series, it changes the whole picture drastically only in the third series. 

In oxides the Mo ion is usually four-coordinated, as, for example, in the most well-known luminescent molybdate CaMo04 with scheelite structure. This, by the way, is the only luminescent molybdate whose luminescence has been investigated in some detail. 

---

From strongly addic solutions benzoin-a-oxime precipitates molybdate and tungstate ions quantitatively chromate, vanadate, niobate, tantalate, and palladium) II) are partially predpitated. The molybdate complex is best ignited at 500-525 °C to Mo03 before weighing alternatively, the predpitate may be dissolved in ammonia solution and the molybdenum predpitated as lead molybdate, in which form it is conveniently weighed. 

Combi cassette. The ColorLock Gold assay kit is based on malachite green-molybdate colorimetric assay, and the yellow reagent turns green in the presence of phosphate. The stabilizer stabilizes acid-labile substrates and the molybdate complex to maintain signal stability. 

Isobutylmalic acid (18) and (— )-2-benzylmalic acid (19), the constituent acids of cornucervine and phalaenopsine La, respectively, have now been shown to have the / -configuration. This was established by a partial asymmetric synthesis of the enantiomers of these acids and comparison of the c.d. spectra of their molybdate complexes with that of the molybdate complex of (-f )-citramalic acid (20) of known S-configuration. 

The same method has been applied with little modification for the determination of silicates in water extract of black liquor and pulp by reducing the molybdate complex with ferrous sulfate in a slightly acidic media [3]. 

The effect of various interfering ions on the molybdate complex must also be considered. Only a very small amount of nitrate can be tolerated, and the permissible chloride concentration depends upon the amount of HCl removed during preparation of the reducing solution (Andersson [1962a]). Molybdate complexes with sulphuric acid when the latter is present in large amounts, and under these conditions, decomposition of the silicomolybdate must occur to a certain extent. Since the heteromolybdates of arsenic and phosphorus are less stable than the corresponding silicomolybdates, interference by these elements can, to some extent, be eliminated by use of polybasic organic acids such as oxalic and tartatic, which form complexes with molybdate. Interference by phosphate, however, cannot be eliminated completely. 

Polarimetric analysis of sorbitol and mannitol in the presence of each other and of sugars is possible because of their enhanced optical rotation when molybdate complexes are formed and the higher rotation of the mannitol molybdate complex under conditions of low acidity (194). The concentration of a pure solution of sorbitol may be determined by means of the refractometer (195). Mass spectra of trimethylsilyl ethers of sugar alcohols provide unambiguous identification of tetritols, pentitols, and hexitols and permit determination of molecular weight (196). 

The method may be standardised, if desired, with pure potassium dihydrogen-orthophosphate (see below) sufficient 1 1 hydrochloric acid must be present to prevent precipitation of quinoline molybdate the molybdophosphate complex is readily formed at a concentration of 20 mL of concentrated hydrochloric acid per 100 mL of solution especially when warm, and precipitation of the quinoline salt should take place slowly from boiling solution. A blank determination should always be made it is mostly due to silica. 

B. Phosphovanadomolybdate method Discussion. This second method is considered to be slightly less sensitive than the previous molybdenum blue method, but it has been particularly useful for phosphorus determinations carried out by means of the Schoniger oxygen flask method (Section 3.31). The phosphovanadomolybdate complex formed between the phosphate, ammonium vanadate, and ammonium molybdate is bright yellow in colour and its absorbance can be measured between 460 and 480 nm. 

Co-extraction of Mo and Cu is potentially a problem with certain feed solutions,14 and again selectivities are very dependent on the nature of modifiers present in formulated reagents.142 The Mo species extracted have not been fully characterized, but may include a neutral dioxo complex, [Mo02L2], which can be assumed to have an N2022 donor set similar to that in the Cu11 complex, and molybdate complexes solvated by neutral phenolic oxime ligands such as [M0O4112 LI l].143 Formation of solvated forms of molybdic acid is supported by evidence that extraction is favorable at very low pH values and that the complexes are readily stripped by aqueous ammonia to produce ammonium molybdate,144... 

The research also revealed new complexities and some questions are still to be answered. The molybdate(VI) system in particular needs further clarification regarding the existence of some polyions. More kinetic and thermodynamic data would also help to improve our understanding of these systems and perhaps lead to a general inclusive explanation of the mechanism of polyoxoanion formation. In this respect the new information about some structural preferences of the different metals in mixed polyoxoanions is of interest and a useful addition to known facts regarding polyoxometalate structures (181). 

Olsen et al. [62] have described a method for the determination of pH8.5 sodium bicarbonate extractable phosphorus in soils. The concentration of the blue complex produced by the reduction, with ascorbic acid, of the phosphomolybdate formed when acid ammonium molybdate reacts with phosphate is measured spectrophotometrically at 880 nm [63]. 

Oxyanions also affect the coordination chemistry of the metal center (84). Molybdate and tungstate are tightly bound noncompetitive inhibitors (Ki s of ca. 4 (iM) (85). These anions bind to the reduced form of the enzyme, changing the rhombic EPR spectrum of the native enzyme to axial (Figure 1) and affecting the NMR shifts observed (84,85). Comparisons of the ENDOR spectra of reduced uterofenin and its molybdate complex show that molybdate binding causes the loss of iH features which are also lost when the reduced enzyme is placed in deuterated solvent (86). These observations suggest that molybdate displaces a bound water upon complexation. 

Hexacyanoferrates were immobilized on Au covered with SAM of 3,3 -thiodipropionic acid [86]. It has been found from voltammetric studies that the surface coverage of hexacyanoferrate is close to one monolayer and such an electrode exhibits very good surface redox behavior. Cheng et al. [87] have described the formation of an extremely thin multilayer film of polybasic lanthanide heteropolytungstate-molybdate complex and cationic polymer of quaternary poly(4-vinylpyridine), partially complexed with osmium bis(2,2 -bipyridine) on a gold electrode precoated with a cysteamine SAM. Consequently, adsorption of inorganic species might also be related to the properties of SAMs. This problem will be discussed in detail in a separate section later. 

In order to interpret these studies we had to postulate a complex between the inert nitrate or perchlorate and the molybdate. I would like to show you some analagous studies we have done in order to justify these complexes and some of the reactions we have obtained with chromate. 

The fact that twelve molybdate ions are bound to each phosphate unit in molybdophosphate has been exploited as an amplifying factor. The molybdophosphoric acid is extracted from the original solution into a mixture of diethyl ether or chloroform with butanol, in order to eliminate the excess of molybdate reagent it is then re-extracted into an aqueous phase and broken down with alkali. The molybdate ions are reacted with ammonium rhodanide90 or aminochlorobenzenethiol76 to give coloured products with absorption maxima at 470 and 710 nm, respectively. One phosphate ion thus yields twelve molybdate units, the optical absorbance is amplified with respect to that of the heteropoly phosphate complex and its measurement provides a sensitive determination procedure. 

---