Palladium vaporization

All known M(COD)2 complexes can now be synthesized on a millimolar scale by the metal atom technique, although both Ni(COD)2 and Pt(COD)2 are more conveniently prepared by conventional synthetic routes (35, 99). The use of palladium vapor to afford Pd(l,5-COD)2 is a straightforward, high-yield (>50% in situ), one-step synthesis, offering advantages over the conventional method if isolation of a... 

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). 

Platinum vapor, (generated by electron beam evaporation of the molten metal at ca. 2x10 torr), or palladium vapor (by evaporation from a resistively heated hearth at ca.l0 torr)) was allowed to dissolve in a solution of poly(isobutyl-aluminoxane), [ C4H9A10]n ... 

Solvated metal vapor deposition Palladium vapors are co-condensed with 1-exene and mesitylene the obtained solution is used for the deposition... 

This structural effect on the chemical shifts of adsorbed molecules is further demonstrated in the NMR spectra of CO on some palladium colloids derived from palladium vapor (see Section 6.2.2.4). If these are amorphous, as suspected, then their metallic properties (conduction bands) which give rise to the Knight shift should therefore not be as well developed. They adsorb CO in a predominantly terminal mode implying a disordered or rough surface (see Section 6.4.3.2), and thus might be expected to be less metallic in the context of this technique. In fact, the C resonance for CO adsorbed on such vapor derived... 

Go-condensation of palladium vapor with l,3-di-jV-/ r/-butylimidazol-2-ylidene provided an alternative synthetic route to a two-coordinate, homoleptic, zero-valent palladium-carbene complex shown in Equation (29). ... 

Koch, R. and Poppa, H. (1987). The influence of the mica surface composition on the growth morphology of discontinuous epitaxial palladium vapor deposits, J. Vac. Sci. Technol. A 5, 1845-1848. 

In a related process, 1,4-dichlorobutene was produced by direct vapor-phase chlorination of butadiene at 160—250°C. The 1,4-dichlorobutenes reacted with aqueous sodium cyanide in the presence of copper catalysts to produce the isomeric 1,4-dicyanobutenes yields were as high as 95% (58). The by-product NaCl could be recovered for reconversion to Na and CI2 via electrolysis. Adiponitrile was produced by the hydrogenation of the dicyanobutenes over a palladium catalyst in either the vapor phase or the Hquid phase (59,60). The yield in either case was 95% or better. This process is no longer practiced by DuPont in favor of the more economically attractive process described below. 

Vapor-phase oxidation over a promoted vanadium pentoxide catalyst gives a 90% yield of maleic anhydride [108-31-6] (139). Liquid-phase oxidation with a supported palladium catalyst gives 55% of succinic acid [110-15-6] (140). 

Vinyl acetate (ethenyl acetate) is produced in the vapor-phase reaction at 180—200°C of acetylene and acetic acid over a cadmium, 2inc, or mercury acetate catalyst. However, the palladium-cataly2ed reaction of ethylene and acetic acid has displaced most of the commercial acetylene-based units (see Acetylene-DERIVED chemicals Vinyl polymers). Current production is dependent on the use of low cost by-product acetylene from ethylene plants or from low cost hydrocarbon feeds. 

Under high pressures and temperatures, iodine reacts with oxygen to form iodine pentoxide [12029-98-0] (44). The reaction of iodine with carbon monoxide under acidic conditions is catalyzed by palladium salts (45). Phosphorous vapor and iodine react to form phosphoms trHodide [13455-01 -17, PI (46). 

Finally, selective hydrogenation of the olefinic bond in mesityl oxide is conducted over a fixed-bed catalyst in either the Hquid or vapor phase. In the hquid phase the reaction takes place at 150°C and 0.69 MPa, in the vapor phase the reaction can be conducted at atmospheric pressure and temperatures of 150—170°C. The reaction is highly exothermic and yields 8.37 kJ/mol (65). To prevent temperature mnaways and obtain high selectivity, the conversion per pass is limited in the Hquid phase, and in the vapor phase inert gases often are used to dilute the reactants. The catalysts employed in both vapor- and Hquid-phase processes include nickel (66—76), palladium (77—79), copper (80,81), and rhodium hydride complexes (82). Complete conversion of mesityl oxide can be obtained at selectivities of 95—98%. 

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. 

Dutch State Mines (Stamicarbon). Vapor-phase, catalytic hydrogenation of phenol to cyclohexanone over palladium on alumina, Hcensed by Stamicarbon, the engineering subsidiary of DSM, gives a 95% yield at high conversion plus an additional 3% by dehydrogenation of coproduct cyclohexanol over a copper catalyst. Cyclohexane oxidation, an alternative route to cyclohexanone, is used in the United States and in Asia by DSM. A cyclohexane vapor-cloud explosion occurred in 1975 at a co-owned DSM plant in Flixborough, UK (12) the plant was rebuilt but later closed. In addition to the conventional Raschig process for hydroxylamine, DSM has developed a hydroxylamine phosphate—oxime (HPO) process for cyclohexanone oxime no by-product ammonium sulfate is produced. Catalytic ammonia oxidation is followed by absorption of NO in a buffered aqueous phosphoric acid... 

Dechlorination can be done in the vapor phase with palladium, platinum, copper, or nickel catalysts (23—26) or in the Hquid phase with palladium catalysts (27). The vapor-phase dechlorination of 1,2,4-trichlorobenzene is reported to give good yields of 1,3-dichlorobenzene (24,26). 

Surfaces. Essentially any electrically conductive surface can be electroplated, although special techniques may be required to make the surface electrically conductive. Many techniques ate used to metalline nonconductive surfaces. These are weU-covered ia the Hterature (3) and can range from coating with metallic-loaded paints or reduced-silver spray, to autocatalytic processes on tin—palladium activated surfaces or vapor-deposited metals. Preparation steps must be optimized and closely controlled for each substrate being electroplated. 

Most of the vinyl acetate produced in the United States is made by the vapor-phase ethylene process. In this process, a vapor-phase mixture of ethylene, acetic acid, and oxygen is passed at elevated temperature and pressures over a fixed-bed catalyst consisting of supported palladium (85). Less than 70% oxygen, acetic acid, and ethylene conversion is realized per pass. Therefore, these components have to be recovered and returned to the reaction zone. The vinyl acetate yield using this process is typically in the 91—95% range (86). Vinyl acetate can be manufactured also from acetylene, acetaldehyde, and the hquid-phase ethylene process (see Vinyl polymers). 

Co-condensation reaction of the vapors of l,3-di-rcrt-butylimidazol-2-ylidene and nickel, palladium, or platinum gives the coordinatively unsaturated 14-electron sandwiches [L M] (M=Ni, Pd, Pt) of the carbene type (990M3228). Palladium(O) carbene complexes can also be prepared by the direct interaction of l,3-R2-imidazol-2-ylidenes (R=/-Pr, r-Bu, Cy, Mes) (L) with the palladium(O) compound [Pd(P(o-Tol)3)2] (OOJOM(595)186), and the product at the first stage is [(L)PdP(o-Tol)3l, and then in excess free carbene [PdL ]. 

An important industrial synthesis of cyclohexanone is by partial hydrogenation of phenol over palladium, carried out in either liquid or vapor phase. 

Fig. 9. Decrease of the catalytic activity of palladium on pumice with time. A— catalytic activity of Pd in initial measurements at 30°C B—catalytic activity of Pd at 30°C after mercury vapor is frozen out C—catalytic activity of Pd at 118°C after removing mercury vapor. (r0)i and (r0) are the initial reaction rates for the first and nth reactions (mm Hg/min). After Mann and Lien (41)-...

E8,6 Use the following vapor pressure data for solid palladium metal as a function of temperature,7 to calculate ASUb//m. the mean enthalpy of sublimation of palladium. 

The hydrogen reduction of the metal halides, described in Sec. 1.2, is generally the favored reaction for metal deposition but is not suitable for the platinum-group metals since the volatilization and decomposition temperatures of their halides are too close to provide efficient vapor transport. 1 1 For that reason, the decomposition of the carbonyl halide is preferred. The exception is palladium which is much more readily deposited by hydrogen reduction than by the carbonyl-halide decomposition. 

Thermal treatment—Processes in which vapor-phase contaminants are destroyed via high-temperature oxidation the primary categories of thermal treatment used to treat MTBE and other oxygenates include thermal oxidation, which employs a flame to generate the high temperatures needed to oxidize contaminants, and catalytic oxidation, which employs lower temperatures in the presence of a catalyst (typically platinum, palladium, or other metal oxides) to destroy contaminants. 

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