Cobalt carbonyl catalytic activity

Within the reaction parameters used, the nickel catalyst is highly selective towards carbonylation. With the exception of trace a-mounts of methane formed, no other hydrogenation product is found. This is in contrast with cobalt whose carbonylation catalytic activity is enhanced by hydrogen but generally associated with aldehyde formation and homologation. 

Carbonyiation of butadiene gives two different products depending on the catalytic species. When PdCl is used in ethanol, ethyl 3-pentenoate (91) is obtained[87,88]. Further carbonyiation of 3-pentenoate catalyzed by cobalt carbonyl affords adipate 92[89], 3-Pentenoate is also obtained in the presence of acid. On the other hand, with catalysis by Pd(OAc)2 and Ph3P, methyl 3,8-nonadienoate (93) is obtained by dimerization-carbonylation[90,91]. The presence of chloride ion firmly attached to Pd makes the difference. The reaction is slow, and higher catalytic activity was observed by using Pd(OAc) , (/-Pr) ,P, and maleic anhydride[92]. Carbonyiation of isoprcne with either PdCi or Pd(OAc)2 and Ph,P gives only the 4-methyl-3-pentenoate 94[93]. 

Susac et al. [33] showed that the cobalt-selenium (Co-Se) system prepared by sputtering and chemical methods was catalytically active toward the ORR in an acidic medium. Lee et al. [34] synthesized ternary non-noble selenides based on W and Co by the reaction of the metal carbonyls and elemental Se in xylenes. These W-Co-Se systems showed catalytic activity toward ORR in acidic media, albeit lower than with Pt/C and seemingly proceeding as a two-electron process. It was pointed out that non-noble metals too can serve as active sites for catalysis, in fact generating sufficient activity to be comparable to that of a noble metal, provided that electronic effects have been induced by the chalcogen modification. 

The hypothesis that the cobalt carbonyl radicals are the carriers of catalytic activity was disproved by a high pressure photochemistry experiment /32/, in which the Co(CO), radical was prepared under hydroformylation conditions by photolysis of dicobalt octacarbonyl in hydrocarbon solvents. The catalytic reaction was not enhanced by the irradiation, as would be expected if the radicals were the active catalyst. On the contrary, the Co(C0)4 radicals were found to inhibit the hydroformylation. They initiate the decomposition of the real active catalyst, HCo(C0)4, in a radical chain process /32, 33/. 

The iodide content of the catalyst formulation is the key to avoiding these problems of competing reactions and achieving maximum acetic acid selectivity. The addition of iodide ensures that any initially formed methanol (7) is rapidly (H) converted to the more electrophilic methyl iodide. However, further increases in the quantities of iodide beyond that needed for methanol conversion to methyl iodide may lead to a portion, or all, of the catalytic-ally active cobalt carbonyl reverting to catalytically inactive cobalt iodide species - e.g. the [Col4] anion identified in this work, or possibly the cationic [Co(MeOH) (CO) I species (9). 

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 predominance of the ruthenium iodocarbonyl over the cobalt carbonyl species in the bimetallic Co-Ru systems is evidenced by the I.R. spectra of the catalytic solutions of the methyl acetate homologation with cobalt and ruthenium catalysts used in about the same concentration or with an excess of ruthenium. The latter compositions actually show the highest activity for the homologation... 

Carbonylation of phenethyl bromide catalysed by Co2(CO)8 alone or modified either with tppts or tppms yielded products of double- and mono-carbonylation, (benzylpyruvic and benzylacetic acid, respectively) at a concentration of 8 mol% cobalt, 85°C and 20 bar CO under basic conditions in an H20/tBuOH (14/1) solvent mixture (Figure 13).475>476 The reaction rates exhibited by Co2(CO)8 were comparable with the Co2(CO)6(tppts)2 catalyst but replacement of tppts by tppms gave rise to a dramatic decrease in catalytic activity.475 Substantially different double/mono carbonylation (d/m ratios) were observed with Co2(CO)8, Co2(CO)e(tppts)2 and Co2(CO)6(tppms)2 7.3, 2.1 and 0.3, respectively, which... 

Y. Kamiya illustrates the influence on catalytic activity of the form of the catalyst. Thus, in the cobalt-catalyzed oxidation of hydrocarbons in acetic acid solution, introduction of bromide ions increases the activity of the catalyst, especially when the metal ion concentration is fairly high. The presence of bromides also results in a marked increase in the proportion of carbonyl compounds among the products and it is believed that these are formed as a result of a propagation step in which bromine-containing cobaltous ions react with alkylperoxy radicals. 

A number of simple and inexpensive materials catalytically promote the cobalt-carbonylation (Reaction 2) in aqueous solution. These include ion-exchange resins, zeolites, or special types of activated carbon. Formation of the active catalyst in a separate reactor is thus economically feasible. The mechanism of this catalysis has not yet been elucidated and seems to differ for each promoter mentioned. After an induction period during which the cobalt fed to the reactor is partially retained by the promoter, fully active materials have absorbed cobalt carbonyl anion Co(CO)4 (ion exchange resins), Co2+ cation (zeolites), or a mixture of Co2+, cobalt carbonyl hydride, and cluster-type cobalt carbonyls (activated carbon). This can be shown by analytical studies (extraction, titration, and IR studies) of active material withdrawn from the reactor. 

The copper(II)-promoted hydrolysis of glycylglycine has been studied in some detail.120 Copper(II) ions catalyze the hydrolysis of glycylglycine in the pH range 3.5 to 6 at 85 °C.120 The pH rate profile has a maximum at pH 4.2, consistent with the view that the catalytically active species in the reaction is the carbonyl-bonded complex. The decrease in rate at higher pH is associated with the formation of a catalytically inactive complex produced by ionization of the peptide hydrogen atom. This view has subsequently been confirmed by other workers,121 in conjunction with an IR investigation of the structures of the copper(II) and zinc(II) complexes in D20 solution.122 Catalysis by cobalt(II),123 and zinc(II), nickel(II) and manganese(II) has also been studied.124-126... 

Duckett and Perutz have shown the stoichiometric reaction of the CpRh(C2H4)(SiR3)H (R = Et, i-Pr) complexes (Scheme 33)201. These complexes have been found to act as precursors to the catalytically active species for the hydrosilylation of ethene with Et3SiH but are not within the catalytic cycle. The mechanism proposed in Scheme 34 for the hydrosilylation of ethene was found to be equivalent to the Seitz-Wrighton hydrosilylation mechanism catalyzed by cobalt carbonyls complexes202. 

In the present review we shall describe recent developments in the catalysis of reactions by dicobalt octacarbonyl. Although many of the reactions to be described do not necessarily involve dicobalt octacarbonyl directly in the catalytic cycle, but some derivative, there are several reasons for choosing this compound as a starting point. The most important reason being that dicobalt octacarbonyl is a reasonably stable, commercially available, fairly well characterized compound which easily gives active catalytic intermediates. Although by no means unique in their catalytic properties, the cobalt carbonyls do provide a particularly active and versatile example of metal carbonyl catalysis. Their catalytic reactions are also by far the most investigated and best understood. 

A high CO pressure would shift equilibrium (4.3) to the left and the catalytic reaction would become slower. In this complex CO is a far better ligand than an alkene. On the other hand the reaction uses CO as a substrate, so it cannot be omitted. Furthermore, low pressures of CO may lead to decomposition of the cobalt carbonyl complexes to metallic cobalt and CO, which is also undesirable. Finally, the product alcohol may stabilize divalent cobalt species which are not active as a catalyst ... 

The synthesis of cobalt carbonyl-boimd silanetriol, Coa(CO)9CSi(OH)a (11) was originally reported by Seyferth et al. (34) by careful hydrolysis of Si—Cl bonds present in Coa(CO)9CSiCla (Scheme 8B). The X-ray crystallographic measurement (35) reveals a cage structure for compound 11. The OH groups present in 11 can be used further for the buildup of a number of heterosiloxanes. The cobalt carbonyl-boimd silanetriol 11 exhibits very high catalytic activity in the hydroformylation of 1-hexene in a biphasic vide infra) system (35). 

Hydroformylation reactions are important from the industrial point of view and the two commonly used hydroformylation catalysts are either Rh or Co based. We thought it would be interesting to anchor a SiOs unit on a cobalt cluster via hydrosilylation. This would be a close model to a silica-supported cobalt cluster. Secondly, since the reactions of silanetriols have been demonstrated to afford three-dimensional metallasiloxanes, we anticipated that this silanetriol would react with substrates such as trialkylaluminums, affording cobalt carbonyl cluster anchored aluminosiloxanes. Such compounds would resemble a modified zeolite having on its surface catalytically active cobalt carbonyl moieties and might inspire the preparation of actual zeolite systems with these modifications. 

Compared with cobalt carbonyl, the phosphine-modified cobalt catalyst introduced by Shell in 1966 leads to an increase of selectivity toward linear products, to an increase in the thermal stability and hydrogenation activity, but also to a lower reactivity. In order to compensate for the lower activity, reaction temperatures have to be kept at about 180 °C. With higher temperatures the n/i selectivity drops [130] as less coordinated cobalt species are involved in the catalytic cycle. The reduced steric demand around the metal center leads to increased formation of branched aldehydes. With respect to formation of by-products, modified cobalt catalysts behave similarly to their unmodified derivatives. 

The cobalt-catalyzed reaction of carbon monoxide and hydrogen with an alkene, hydroformylation, is an extremely important industrial process, but it occurs under vigorous conditions (200-400 bar, 150-200 °C) and is not a particularly selective reaction. In the presence of ligand-modified rhodium catalysts, however, hydroformylation can be carried out under extremely mild conditions (1 bar, 25 C). The catalytic activity of such rhodium complexes is in fact lO -Ky times greater than that of cobalt complexes and side reactions, such as hydrogenation, are significantly reduced. The reactivity of alkenes in hydroformylation follows a similar pattern to that observed in other carbonylation reactions, i.e. linear terminal alkenes react more readily than linear internal alkenes, which in turn are more reactive than branched... 

The selective production of methanol and of ethanol by carbon monoxide hydrogenation involving pyrolysed rhodium carbonyl clusters supported on basic or amphoteric oxides, respectively, has been discussed. The nature of the support clearly plays the major role in influencing the ratio of oxygenated products to hydrocarbon products, whereas the nuclearity and charge of the starting rhodium cluster compound are of minor importance. Ichikawa has now extended this work to a study of (CO 4- Hj) reactions in the presence of alkenes and to reactions over catalysts derived from platinum and iridium clusters. Rhodium, bimetallic Rh-Co, and cobalt carbonyl clusters supported on zinc oxide and other basic oxides are active catalysts for the hydro-formylation of ethene and propene at one atm and 90-180°C. Various rhodium carbonyl cluster precursors have been used catalytic activities at about 160vary in the order Rh4(CO)i2 > Rh6(CO)ig > [Rh7(CO)i6] >... 

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