Cobalt vaporization

A model similar to that of the iron complex 31 was proposed for the cobalt species synthesized as a result of co-condensation of cobalt vapors with pyrrole in vacuum. A frozen matrix formed is subsequently warmed to room temperature (89JA3881). An oligomer or a polymer results, in which a- and ir-donor functions are realized simultaneously. The model proposed differs from that for the iron pyrrolyl complex by inclusion of the Co—Co bonds to attain the 18-electron configuration. 

Cobalt vapor interacts with norbornene to produce Co(C7H10)3, a 15-electron complex, apparently isostructural with Ni(C7H10)3. The cobalt complex is soluble in hydrocarbon solvents to afford deep blue solutions decomposing rapidly and autocatalytically at -15° (5a, 134). It has not yet been possible to isolate this complex in a pure state but some of the reactions have been examined by trapping experiments ... 

Some of these derivatives are useful catalysts for the codimerization of dienes with acrylic esters (82, 138, 140, 143). The reaction between cobalt vapor and butadiene is complex, and the nature of the products remains to be elucidated. However, there is a report of the synthesis of the yellow complex HCo(C4H6)2 from the condensation of a mixture of C4H and Me3CH with cobalt vapor (104, 110). 

Other reactions of dienes with metal atoms are only of a limited synthetic use. Dibenzylideneacetone (PhCH=CH—CO—CH=CHPh DBA) reacts with palladium vapor to afford Pd2(DBA)3, a complex in which the coordination is through the two C=C units and does not involve the C=0 (5, 92). Cobalt vapor undergoes an extremely complicated reaction with 1,4-pentadiene, producing pentenes, C5H6, and various polymers as well as the organometallic product, HCo( 1,3-pen tadiene)2, which involves isomerization from a nonconjugated to a conjugated diene (104, 110). 

Cobalt vapor was generated by directly heating a 0.01-in. ribbon filament of the metal and cocondensed with C2H4/Ar matrices at 12-15K. A series of mono- and binuclear cobalt-ethylene complexes Co(C2H4) (where / = 1, 2) and Co2(C2H4)OT (where m = 1, 2) as well as a suspected tetranuclear species Co4(C2H4)f have been detected by spectroscopic methods. 

Yamazaki s complex (Structure 5) contains two alkyne molecules linked together to form a five-membered metallacycle. Arene-solvated cobalt atoms, obtained by reacting cobalt vapor and arenes, have been used by Italian workers to promote the conversion of a,w-dialkynes and nitriles giving alkynyl-substituted pyridines [20]. -Tolueneiron(0) complexes have also been utilized for the co-cyclotrimerization of acetylene and alkyl cyanides or benzonitrile giving a-substituted pyridine derivatives. However, the catalytic transformation to the industrially important 2-vinylpyridine fails in this case acrylonitrile cannot be co-cyclotrimerized with acetylene at the iron catalyst [17]. 

Because they have low vapor pressures, transition metals cannot be loaded by direct adsorption, but their adsorption can be mediated by transient organo-metallic complexes formed between zerovalent metal atoms and solvent molecules. This is the basis of the solvated metal atom dispersion (SMAD) method developed by Klabunde and Tanaka [72]. Metal vapors condensed in Hquid hydrocarbons at low temperatures form weak complexes that are easily decomposed even below room temperature. Microporous supports impregnated with solutions of metal complexes at low temperatures are warmed up to decompose the complex and liberate zerovalent metal atoms which nucleate into clusters. Preparation of Ni- and Co-clusters in HY and HZSM-5 was reported [72]. In the same way, Nazar et al. [64] condensed iron and cobalt vapors in a slurry of dehydrated NaY zeolite in toluene at -120 °C, then the mixture was rotated at-78°C. The bis-toluene complex thus formed and adsorbed in the zeoUte was decomposed by warming to room temperature yielding clusters small enough to fit into supercages. 

High purity acetaldehyde is desirable for oxidation. The aldehyde is diluted with solvent to moderate oxidation and to permit safer operation. In the hquid take-off process, acetaldehyde is maintained at 30—40 wt % and when a vapor product is taken, no more than 6 wt % aldehyde is in the reactor solvent. A considerable recycle stream is returned to the oxidation reactor to increase selectivity. Recycle air, chiefly nitrogen, is added to the air introducted to the reactor at 4000—4500 times the reactor volume per hour. The customary catalyst is a mixture of three parts copper acetate to one part cobalt acetate by weight. Either salt alone is less effective than the mixture. Copper acetate may be as high as 2 wt % in the reaction solvent, but cobalt acetate ought not rise above 0.5 wt %. The reaction is carried out at 45—60°C under 100—300 kPa (15—44 psi). The reaction solvent is far above the boiling point of acetaldehyde, but the reaction is so fast that Httle escapes unoxidized. This temperature helps oxygen absorption, reduces acetaldehyde losses, and inhibits anhydride hydrolysis. 

Heterogeneous vapor-phase fluorination of a chlorocarbon or chlorohydrocarbon with HP over a supported metal catalyst is an alternative to the hquid phase process. Salts of chromium, nickel, cobalt or iron on an A1P. support are considered viable catalysts in pellet or fluidized powder form. This process can be used to manufacture CPC-11 and CPC-12, but is hampered by the formation of over-fluorinated by-products with Httle to no commercial value. The most effective appHcation for vapor-phase fluorination is where all the halogens are to be replaced by fluorine, as in manufacture of 3,3,3-trifluoropropene [677-21 ] (14) for use in polyfluorosiHcones. 

Eigure 3 is a flow diagram which gives an example of the commercial practice of the Dynamit Nobel process (73). -Xylene, air, and catalyst are fed continuously to the oxidation reactor where they are joined with recycle methyl -toluate. Typically, the catalyst is a cobalt salt, but cobalt and manganese are also used in combination. Titanium or other expensive metallurgy is not required because bromine and acetic acid are not used. The oxidation reactor is maintained at 140—180°C and 500—800 kPa (5—8 atm). The heat of reaction is removed by vaporization of water and excess -xylene these are condensed, water is separated, and -xylene is returned continuously (72,74). Cooling coils can also be used (70). 

The predominant process for manufacture of aniline is the catalytic reduction of nitroben2ene [98-95-3] ixh. hydrogen. The reduction is carried out in the vapor phase (50—55) or Hquid phase (56—60). A fixed-bed reactor is commonly used for the vapor-phase process and the reactor is operated under pressure. A number of catalysts have been cited and include copper, copper on siHca, copper oxide, sulfides of nickel, molybdenum, tungsten, and palladium—vanadium on alumina or Htbium—aluminum spinels. Catalysts cited for the Hquid-phase processes include nickel, copper or cobalt supported on a suitable inert carrier, and palladium or platinum or their mixtures supported on carbon. 

Hydrogen sulfide has been produced in commercial quantities by the direct combination of the elements. The reaction of hydrogen and sulfur vapor proceeds at ca 500°C in the presence of a catalyst, eg, bauxite, an aluminosihcate, or cobalt molybdate. This process yields hydrogen sulfide that is of good purity and is suitable for preparation of sodium sulfide and sodium hydrosulfide (see Sodium compounds). Most hydrogen sulfide used commercially is either a by-product or is obtained from sour natural gas. 

The oxidation of cyclohexane to a mixture of cyclohexanol and cyclohexanone, known as KA-od (ketone—alcohol, cyclohexanone—cyclohexanol cmde mixture), is used for most production (1). The earlier technology that used an oxidation catalyst such as cobalt naphthenate at 180—250°C at low conversions (2) has been improved. Cyclohexanol can be obtained through a boric acid-catalyzed cyclohexane oxidation at 140—180°C with up to 10% conversion (3). Unreacted cyclohexane is recycled and the product mixture is separated by vacuum distillation. The hydrogenation of phenol to a mixture of cyclohexanol and cyclohexanone is usually carried out at elevated temperatures and pressure ia either the Hquid (4) or ia the vapor phase (5) catalyzed by nickel. 

Oxidation catalysts are either metals that chemisorb oxygen readily, such as platinum or silver, or transition metal oxides that are able to give and take oxygen by reason of their having several possible oxidation states. Ethylene oxide is formed with silver, ammonia is oxidized with platinum, and silver or copper in the form of metal screens catalyze the oxidation of methanol to formaldehyde. Cobalt catalysis is used in the following oxidations butane to acetic acid and to butyl-hydroperoxide, cyclohexane to cyclohexylperoxide, acetaldehyde to acetic acid and toluene to benzoic acid. PdCh-CuCb is used for many liquid-phase oxidations and V9O5 combinations for many vapor-phase oxidations. 

C.-H. Kiang e o/.[33] reported that the singlelayered coiled lubes were obtained by co-vaporizing cobalt with carbon in an arc fullerene generator. A single-layered helical structure with radii of curvature as small as 20 nm was seen. These helically coiled forms lend to bundle together. In the soot obtained with sulfur-containing anodes, they also found the 1.3-nm diameter lube coil around the 3.6 nm tube (see Fig. 14). This kind of structure was theoretically proposed in ref. [14]. 

Perfluoroalkyl or -aryl halides undergo oxidative addition with metal vapors to form nonsolvated fluonnated organometallic halides and this topic has been die subject of a review [289] Pentafluorophenyl halides react with Rieke nickel, cobalt, and iron to give bispentafluorophenylmetal compounds, which can be isolated in good yields as liquid complexes [290] Rieke nickel can also be used to promote the reaction of pentafluorophenyl halides with acid halides [297] (equation 193)... 

The metal-vapor technique was applied to cobalt atoms and r-BuC = P (01JOM(635)212). The mixture of products that resulted includes the mixed-ligand sandwiches 170 and 171. Further interaction of complex 170 with [W(C0)5(THF)] leads to the coordination of the W(CO)5-group via the phosphorus heteroatom of the four-membered ring to yield 172. 

Clausius-Clapeyron equation An equation expressing the temperature dependence of vapor pressure ln(P2/Pi) = AHvapCl/Tj - 1/T2)/R, 230,303-305 Claussen, Walter, 66 Cobalt, 410-411 Cobalt (II) chloride, 66 Coefficient A number preceding a formula in a chemical equation, 61 Coefficient rule Rule which states that when the coefficients of a chemical equation are multiplied by a number n, the equilibrium constant is raised to the nth power, 327... 

Acetylene compounds Dicobaltoctacarbonyl Formation of colored complexes. After the reagent excess has been washed out, reaction with bromine vapor yields cobalt bromide, which reacts with a-nitroso-P-naphthol to yield red chromatogram zones on an almost colorless background. [11]... 

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