Acetic acid cobalt complexes

Most of the catalysts employed in the chemical technologies are heterogeneous. The chemical reaction takes place on surfaces, and the reactants are introduced as gases or liquids. Homogeneous catalysts, which are frequently metalloorganic molecules or clusters of molecules, also find wide and important applications in the chemical technologies [24]. Some of the important homogeneously catalyzed processes are listed in Table 7.44. Carbonylation, which involves the addition of CO and H2 to a C olefin to produce a + 1 acid, aldehyde, or alcohol, uses rhodium and cobalt complexes. Cobalt, copper, and palladium ions are used for the oxidation of ethylene to acetaldehyde and to acetic acid. Cobalt(II) acetate is used mostly for alkane oxidation to acids, especially butane. The air oxidation of cyclohexane to cyclohexanone and cyclohexanol is also carried out mostly with cobalt salts. Further oxidation to adipic acid uses copper(II) and vanadium(V) salts as catalysts. The... 

In 1996, consumption in the western world was 14.2 tonnes of rhodium and 3.8 tonnes of iridium. Unquestionably the main uses of rhodium (over 90%) are now catalytic, e.g. for the control of exhaust emissions in the car (automobile) industry and, in the form of phosphine complexes, in hydrogenation and hydroformylation reactions where it is frequently more efficient than the more commonly used cobalt catalysts. Iridium is used in the coating of anodes in chloralkali plant and as a catalyst in the production of acetic acid. It also finds small-scale applications in specialist hard alloys. 

The cobalt complex is usually formed in a hot acetate-acetic acid medium. After the formation of the cobalt colour, hydrochloric acid or nitric acid is added to decompose the complexes of most of the other heavy metals present. Iron, copper, cerium(IV), chromium(III and VI), nickel, vanadyl vanadium, and copper interfere when present in appreciable quantities. Excess of the reagent minimises the interference of iron(II) iron(III) can be removed by diethyl ether extraction from a hydrochloric acid solution. Most of the interferences can be eliminated by treatment with potassium bromate, followed by the addition of an alkali fluoride. Cobalt may also be isolated by dithizone extraction from a basic medium after copper has been removed (if necessary) from acidic solution. An alumina column may also be used to adsorb the cobalt nitroso-R-chelate anion in the presence of perchloric acid, the other elements are eluted with warm 1M nitric acid, and finally the cobalt complex with 1M sulphuric acid, and the absorbance measured at 500 nm. 

In acetic acid, the reaction of cobalt ions with ROOH proceeds via two channels through the mono- and binuclear cobalt complexes. 

Jensen was the first to report in 1983 that the color of the solution oscillated between pink and dark brown in the presence of cobalt(II) and bromide ions when the reaction was carried out in a 90/10 (w/w) acetic acid/water mixture (162). This color change was accompanied by a change in the redox potential and the oscillations were observed for over 16 h and 800 cycles. Presumably, the pink color corresponds to a low Co(III)/Co(II) ratio, the dark brownish black to a high Co(III)/Co(II) ratio or to a Co(III)Br complex in this reaction. 

A cobalt complex containing this type of ligand is effective in the sodium borohydride-mediated enantioselective reduction of a variety of a,/ -unsaturated carboxylates. As can be seen from Scheme 6-8, in the presence of a catalytic amount of a complex formed in situ from C0CI2 and chiral ligand 11, reduction proceeds smoothly, giving product with up to 96% ee. The chiral ligand can easily be recovered by treating the reaction mixture with acetic acid. 

A second manufacturing method for acetic acid utilizes butane from the C4 petroleum stream rather than ethylene. It is a very complex oxidation with a variety of products formed, but conditions can be controlled to allow a large percentage of acetic acid to be formed. Cobalt (best), manganese, or chromium acetates are catalysts with temperatures of 50-250 °C and a pressure of 800 psi. 

Ruthenium, cobalt and halogen are the key elements of this catalysis (2), although ruthenium in combination with halogen-containing zirconium and titanium derivatives is also effective (3). In the case of the Ru-Oo couple, the highest yields of acetic acid may generally be achieved with ruthenium oxide, carbonyls and complex derivatives in combination with various cobalt halides dispersed in low-melting quaternary phosphonium halide salts (2). 

Hydrogenation of acetic anhydride to acetaldehyde (equation 23) has been demonstrated utilizing cobalt carbonyl under one atmosphere of hydrogen. However, the cobalt complex is short lived. A more efficient cobalt catalyzed reaction with substantial catalyst longevity was realized at a temperature of 190 and 3000 psi pressure CO and hydrogen. The main products were equal amounts of EDA and acetic acid. Upon investigation, this reaction was found exceptionally efficient at a more reasonable 1500 psi pressure provided that the temperature was maintained... 

Carbonylation of methanol to form acetic acid has been performed industrially using carbonyl complexes of cobalt ( ) or rhodium (2 ) and iodide promoter in the liquid phase. Recently, it has been claimed that nickel carbonyl or other nickel compounds are effective catalysts for the reaction at pressure as low as 30 atm (2/4), For the rhodium catalyst, the conditions are fairly mild (175 C and 28 atm) and the product selectivity is excellent (99% based on methanol). However, the process has the disadvantages that the proven reserves of rhodium are quite limited in both location and quantity and that the reaction medium is highly corrosive. It is highly desirable, therefore, to develop a vapor phase process, which is free from the corrosion problem, utilizing a base metal catalyst. The authors have already reported that nickel on activated carbon exhibits excellent catalytic activity for the carbonylation of... 

The crude substance is their recrystallised from water containing acetic acid. The compound was originally believed to exist in two isomeric forms, but Jorgensen found the crystalline form depends on the concentration of acetic acid used for crystallisation, inasmuch as rhombic leaflets separate from hot dilute acetic acid, and from hot concentrated acid the substance separates in yellow-brown needles. The complex is sparingly soluble in water, and gives no precipitate in aqueous solution with silver nitrate or potassium chromate. If treated with cold hydrochloric acid it is transformed into chloro-dinitro-triammino cobalt, [Co(NH3)3(N02)2Cl], and if warmed with concentrated hydrochloric acid gives diehloro-aquo-triammino-cobaltic chloride. 

Noncatalytic oxidation to produce acetic acid can be carried out in the gas phase (350-400°C, 5-10 atm) or in the liquid phase (150-200°C). Liquid-phase catalytic oxidations are operated under similar mild conditions. Conditions for the oxidation of naphtha are usually more severe than those for n-butane, and the process gives more complex product mixtures.865-869 Cobalt and other transition-metal salts (Mn, Ni, Cr) are used as catalysts, although cobalt acetate is preferred. In the oxidation carried out in acetic acid solution at almost total conversion, carbon oxides, carboxylic acids and esters, and carbonyl compounds are the major byproducts. Acetic acid is produced in moderate yields (40-60%) and the economy of the process depends largely on the sale of the byproducts (propionic acid, 2-butanone). 

When the cobalt salt of carboxylic acid and bromide ion are dissolved in acetic acid, a cobalt bromide complex is formed instantaneously. For cobalt dibromide a pronounced induction period was observed, but adding sodium acetate eliminates entirely the induction period, suggesting that cobalt monobromide is responsible for the catalysis. 

Dr. Kamiya has attempted to explain the role of the catalyst according to Reactions 13-15, and he has attempted to differentiate between these proposed reaction steps and the simplified Reactions 3 and 4. It is not clear to me what types of structures he is trying to portray by using the empirical formulae Co2+BrH and Co3+Br". There does not seem to be any evidence for any unusual complexes in these solutions, and there does not seem to be any need to postulate them. It really becomes a matter of semantics because nobody believes that in solution Br, for example, exists as such, but it must be solvated by or coordinated with other species. Dr. Kamiya also implies that the initiation step is a direct reaction of the hydrocarbon with Co (III) ion. To my knowledge, a reaction such as this in acetic acid solution has never been demonstrated. We have shown that the reaction between cobalt (III) acetate in acetic acid and toluene is negligibly slow. It would be more likely to consider the reaction... 

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