Oxidation products of the metals

A redetermination of the structure of the commonly encountered oxidation product of the metal complexing agent dithizone (PhN=NC(S)NHNHPh) has confirmed it to be 3-phenylazo-l//-4,1,2-benzothiadiazine (21) <69CC392, 82AJC2157). The crystals of the azo-compound are orthorhombic and the substantially planar molecule is present as the 1 //-tautomer in the solid state. 

Although the elements tantalum and niobium were discovered more than 200 years ago in the form of oxides, the true beginning of the chemistry of tantalum and niobium was the discovery and investigation of complex fluorotantalates and fluoroniobates of alkali metals. Application of complex fluoride compounds enabled the separation of tantalum and niobium and in fact initiated the development of the industrial production of the metals and their compounds. 

Yields in the above reactions can often be improved by the addition of 1 mole of triphenylphosphine directly to the trifluoroacetic acid solution of the reactants immediately before final work-up. It would appear that the triphenylphosphine functions as a scavenger for TTFA released in the metal-metal exchange reaction, thus protecting the final phenol from further electrophilic thallation and/or oxidation. Validation of the metal-metal exchange mechanism was obtained indirectly by isolation and characterization of an ArTlX2/LTTFA complex directly from the reaction mixture. NMR analysis revealed that this complex still possessed an intact aryl-thallium bond, indicating that it was probably the precursor to the transmetallation products, an aryllead tristrifluoroacetate and TTFA. 

A detailed study of the mechanism of the insertion reaction of monomer between the metal-carbon bond requires quantitative information on the kinetics of the process. For this information to be meaningful, studies should be carried out on a homogeneous system. Whereas olefins and compounds such as Zr(benzyl)4 and Cr(2-Me-allyl)3, etc. are very soluble in hydrocarbon solvents, the polymers formed are crystalline and therefore insoluble below the melting temperature of the polyolefine formed. It is therefore not possible to use olefins for kinetic studies. Two completely homogeneous systems have been identified that can be used to study the polymerization quantitatively. These are the polymerization of styrene by Zr(benzyl)4 in toluene (16, 25) and the polymerization of methyl methacrylate by Cr(allyl)3 and Cr(2-Me-allyl)3 (12)- The latter system is unusual since esters normally react with transition metal allyl compounds (10) but a-methyl esters such as methyl methacrylate do not (p. 270) and the only product of reaction is polymethylmethacrylate. Also it has been shown with both systems that polymerization occurs without a change in the oxidation state of the metal. 

Therefore, other factors that have not yet been studied and are not easily quantifiable, such as the absorption properties of the C.-T. adduct at the surface of the metal powder and the solubility of the formed species should be important in determining the oxidation properties of C.-T. adducts towards metal powders. Furthermore, some extrinsic factors inherent to the experimental conditions, such as reaction temperature, reagent concentration, and nature of the solvent have been reported to affect the overall yield or the course of the reaction, and led to separation of different products in some cases.55 59 In any case, it appears that the simultaneous presence of the donor molecule and the di-/inter-halogen lowers the oxidation potentials of the metals, allowing their oxidation, dissolution, and complexation. 

The reaction of benzene with Cu(II) and Fe(III)-exchanged hectorites at elevated temperatures produced a variety of organic radical products, depending on the concentration of water in the reaction medium and the reaction time (90). The formation of free radicals was accompanied by a reduction in oxidation state of the metals, a process that had a zero-order dependence on the metal ion concentration. Under anhydrous conditions the free radicals appeared to populate sites in the interlayer region, the activation energies under these conditions being lower than in the hydrated samples. 

Most industrially desirahle oxidation processes target products of partial, not total oxidation. Well-investigated examples are the oxidation of propane or propene to acrolein, hutane to maleic acid anhydride, benzene to phenol, or the ammoxidation of propene to acrylonitrile. The mechanism of many reactions of this type is adequately described in terms of the Mars and van Krevelen modeE A molecule is chemisorbed at the surface of the oxide and reacts with one or more oxygen ions, lowering the electrochemical oxidation state of the metal ions in the process. After desorption of the product, the oxide reacts with O2, re-oxidizing the metal ions to their original oxidation state. The selectivity of the process is determined by the relative chances of... 

These oxidations suffer from the fact that the high selectivities are only observed at low conversions (<7%). At higher conversions, the carboxylic acid products leach the transition metals out of the zeolite framework into solution where the selectivity index is much lower [63]. As these reactions proceed, the 3 -I- oxidation states of the metal ions return to their 2 -I- states, accompanied by their characteristic color change. In the case of MnAlPO-18, the spent catalyst (Mn ) was washed with methanol and reactivated in dry air at 550°C and successfully recycled (Mn Mn ) twice without appreciable loss of activity [64]. 

The molecular mass of the combustion products in the ramburner is increased by the formation of the oxidized metal particles. However, the temperature in the ramburner is also increased by the oxidation. The results of thermochemical calculations indicate that the specific impulse generated by the combustion in the ramburner is more dependent on the average combustion temperature than the average molecular mass of the products when metal particles are added. Table 15.4 shows the heats of combustion and the major oxidized products of the soHd particles used in ducted rockets. 

The metallic arsenic is obtained primarily from its mineral, arsenopyrite. The mineral is smelted at 650 to 700°C in the absence of air. However, the most common method of production of the metal involves reduction of arsenic trioxide, AsOs with charcoal. Arsenic trioxide is produced by oxidation of arsenic present in the lead and copper concentrates during smelting of such concentrates. The trioxide so formed, readily volatilizes and is collected in a dust flue system where further treatment and roasting can upgrade the trioxide content. The trioxide vapors are then condensed and further purified by pressure leaching and recrystallization techniques. It is then reduced with charcoal to give metallic arsenic. 

Of course it can be argued that the growth we are now seeing merely represents the logical development of the industry once having achieved commercial success in high volume separation of pure oxides by solvent extraction it would seem only natural that the industry should then turn its attention to large scale production of the metals. But in practice it has not worked out that... 

These reactions are two examples of a process used for obtaining metals from oxides, in which the metal is said to be reduced9. Since technical processes are concerned only with the production of the metal they are called reduction processes, overlooking the fact that hydrogen is oxidized during the reaction. Actually, these reactions consist of the substitution of one positive ion in an oxide by another. From the stability rules it is possible to predict which metal will... 

In this generic example, the oxidation state of the metal is reduced by two, while the product is released in the reductive elimination step. In many reactions the oxidative addition does not provide the proper stereochemistry for elimination an isomerization must occur. 

Solid /8-CrPc reacts reversibly with gaseous NO at ambient temperature to give a 1 1 adduct, which reacts with both py and 02 (Scheme 117).596 No structural information is available on the oxidation product of the nitrosyl complex. In contrast to the /3 form, solid ar-CrPc is unreactive towards either 02 or NO, a difference ascribed to the solid-state structures of the two polymorphs.597 Although the distance between the phthalocyanine planes is similar (340 pm), in both cases the metal-metal distance increases from 340 to 480 pm on going from the a to the /3 form. These distances are sufficient to permit access of 02 or NO in the /8 form, while excluding them from the a form. The addition of py to CrPc(NO) causes the NO stretching band in the IR spectrum to intensify and to sharpen considerably. The diffuse nature of this band in CrPc(NO) indicates the presence of a perturbed NO ligand but the introduction of py causes lattice expansion and eliminates the perturbation. 

The product elimination step proceeds with cleavage of the catalyst-substrate bonds. This may occur by dissociation, solvolysis, or a coupling of substrate moieties to form the product. The last of these involves covalent bond formation within the product, and corresponds to the microscopic reverse of oxidative addition. Upon reductive elimination both the coordination number and formal oxidation state of the metal complex decrease. In most homogeneous catalytic processes, the product elimination step, while essential, is usually not rate determining. The larger kinetic barriers are more frequently encountered in substrate activation and/or transformation. 

In acid-base neutralization reactions, no change occurs in the oxidation number of the metal cation. In the above reactions, for example, there is no change in the oxidation number of sodium which remains in +1 oxidation state, both in the reactant and the product. 

---