Cis-Unsaturated fatty acid products by hydrogenation with chromium hexacarbonyl

The use of Cr(CO)₆ was investigated to convert polyunsaturated fats intocis unsaturated products. With methyl sorbate, the same order of selectivity for the formation ofcis-3-hexenoate was demonstrated for Cr(CO)₆ as for the arene-Cr(CO)₃ complexes. With conjugated fatty esters, the stereoselectivity of Cr(CO)₆ toward thetrans, trans diene system was particularly high in acetone. However, this solvent was not suitable at elevated temperatures required to hydrogenatecis, trans- andcis, cis-conjugated dienes (175 C) and nonconjugated soybean oil (200 C). Reaction parameters were analyzed statistically to optimize hydrogenation of methyl sorbate and soybean oil. To achieve acceptable oxidative stability, it is necessary to reduce the linolenate constituent of soybean oil below 1–3%. When this is done commercially with conventional heterogenous catalysts, the hydrogenated products contain more than 15%trans unsaturation. By hydrogenating soybean oil with Cr(CO)₆ (200 C, 500 psi H₂, 1% catalyst in hexane solution), the product contains less than 3% each of linolenate andtrans unsaturation. Recycling of Cr(CO)₆ catalyst by sublimation was carried through three hydrogenations of soybean oil, but, about 10% of the chromium was lost in each cycle by decomposition. The hydrogenation mechanism of Cr(CO)₆ is compared with that of arene-Cr(CO)₃ complexes. Presented in part at Seventh Conference on Catalysis in Organic Syntheses, Chicago, Illinois, June 5–7, 1978.     

Cr(CO)3-complexed,silica-bonded polyphenylsiloxane as a stereoselective catalyst for hydrogenation of sorbate and soybean methyl esters

A silica-bonded complex was prepared by reacting polyphenylsiloxane with silylated Chromosorb and then with Cr(CO)₆. This complex catalyzed stereoselective hydrogenation of sorbate tocis-3-hexenoate. Soybean methyl esters were hydrogenated at 210 C in cyclohexane to form products high incis unsaturation. The recovered catalyst could be recycled once with methyl sorbate. IR showed decreased Cr(CO)₃ in the recovered catalysts, and the hydrogenation products contained inactive Cr.     

Homogeneous catalytic hydrogenation of unsaturated fats: Group VIB metal carbonyl complexes

Carbonyl complexes of Cr, Mo and W have been studied as soluble catalysts for the hydrogenation of methyl sorbate and of methyl esters from soybean oil. With methyl sorbate, relative catalytic activity decreased in the approximate order: mesitylene-Mo(CO)₃, cycloheptatriene-Mo(CO)₃, cycloheptatriene-Cr(CO)₃, bicyclo (2,2,1) hepta-2,5-diene-Mo(CO)₄, chlorobenzene-Cr(CO)₃, methyl benzoate-Cr(CO)₃, mesitylene-W(CO)₃, benzene-Cr(CO)₃, toluene-Cr(CO)₃, mesitylene-Cr(CO)₃, and hexamethylbenzene-Cr(CO)₃. Order of catalytic activity was related to thermal stability of the complexes during hydrogenation. With mesitylene-M(CO)₃ complexes, selectivity varied in the order Cr>Mo>W. Under certain conditions the mesitylene complexes of W, Cr and Mo reduced methyl sorbate respectively to methyl 2-, 3-, and 4-hexenoates as main products. The more active and thermally stable Cr(CO)₃ complexes catalyzed effectively the hydrogenation of linoleate and linolenate in soybean oil esters with little or no stearate formation. The hydrogenated products formed with the benzoate complex at 165–175 C contained 50–67% monoene, 18–30% diene, 2–7% conjugated diene, and only 3–7%trans unsaturation. Linolenate-linoleate selectivity values varied from 3 to 5 and linoleate-oleate selectivity from 7 to 80. Monoene fractions had 40–50% of the double bond in the C-9 position; the rest of the unsaturation was distributed mainly between the C-10 and C-12 positions. Conjugation is apparently an intermediate step in the hydrogenation of linoleate and linolenate. The Cr(CO)₃ complexes are unique in catalyzing the hydrogenation of polyunsaturated fatty esters to monounsaturated fatty esters of lowtrans content. Presented at AOCS-AACC Joint Meeting, Washington, D.C. April, 1968. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Selective homogeneous hydrogenation of triunsaturated fats catalyzed by tricarbonyl chromium complexes

The need for a selective catalyst to hydrogenate linolenate in soybean oil has prompted our continuing study of various model triunsaturated fats. Hydrogenation of methylβ-eleostearate (methyltrans,trans,trans-9,11,13-octadecatrienoate) with Cr(CO)₃ complexes yielded diene products expected from 1,4-addition (trans-9,cis-12- andcis-10,trans-13-octadecadienoates). Withα-eleostearate (cis,trans,trans-9,11,13-octadecatrienoate), stereoselective 1,4-reduction of thetrans,trans-diene portion yielded linoleate (cis,cis-9,12-octadecadienoate). However,cis,trans-1,4-dienes were also formed from the apparent isomerization ofα- toβ-eleostearate. Hydrogenation of methyl linolenate (methylcis,cis,cis-9,12,15-octadecatrienoate) produced a mixture of isomeric dienes and monoenes attributed to conjugation occurring as an intermediate step. The hydrogenation ofα-eleostearin in tung oil was more stereoselective in forming thecis,cis-diene than the corresponding methyl ester. Hydrogenation of linseed oil yielded a mixture of dienes and monoenes containing 7%trans unsaturation. We have suggested how the mechanism of stereoselective hydrogenation with Cr(CO)₃ catalysts can be applied to the problem of selective hydrogenation of linolenate in soybean oil. No. Market. Nutr. Res. Div., ARS, USDA.     

Homogenous catalytic conjugation of polyunsaturated fats by chromium carbonyls

Various arene-Cr (CO)₃ complexes and Cr(CO)₆ are effective soluble catalysts for the conjugation of polyunsaturated fats. Methyl benzoate-Cr(CO)₃ is one of the most active catalysts. The following conjugation levels were obtained: methyl linoleate, 65%; methyl linolenate, 45%; the polyunsaturates in soybean and safflower oils, 73%; and in linseed oil 48%. Conjugated dienes from linoleate were predominantlycis,trans in configuration. Their double bonds were distributed between C₅ and C₁₆ of the fatty acid chain. Hydrogenation and dehydrogenation are side reactions, which seem to limit the yield of conjugated dienes from methyl linoleate. A conjugation mechanism is proposed that involves allyl-HCr(CO)₃ complexes as intermediates undergoing 1,3- and 1,5-hydrogen shifts. Presented at the AOCS Meeting, San Francisco, April 1969. No, Utiliz. Res. Dev. Div., ARS, USDA.     

Photo-activated metal carbonyl complexes as stereoselective catalysts for the homogeneous hydrogenation of dienes

Significantly increased activity of Cr(CO)₆ was achieved for the stereoselective homogeneous hydrogenation of methyl sorbate andtrans,trans-conjugated fatty esters at ambient temperature and pressure by exposing the catalyst to UV irradiation (3500 Å) in a solvent mixture of cyclohexane-acetonitrile (20:1). In this solvent mixture, methyl sorbate was converted quantitatively at ambient conditions into methylcis-3-hexenoate, and methyltrans-9,trans-11-octadecadienoate into methylcis-10-octadecenoate (99.9%). These products are expected by 1,4-addition of hydrogen. Under these conditions no hydrogenation of methyl linoleate occurred. Under the same conditions, cycloheptatriene-Cr(CO)₃ showed lower activity than Cr(CO)₆, and Mo(CO)₆ and mesitylene-Mo(CO)₃ showed no significant activity toward conjugated substrates. When Cr(CO)₆ and Mo(CO)₆ were irradiated at 2537 Å they caused the geometric isomerization of methyl sorbate without hydrogenation, but had no effect on methyl linoleate. A hydrogenation mechanism is proposed for Cr(CO)₆ that involves CH₃CN- and H₂-Cr(CO)₃ complexes as intermediates for the stereoselective 1,4-addition of hydrogen totrans,trans-conjugated dienes.     

Functional gel-type resin based palladium catalysts: The role of polymer properties in the hydrogenation of the CC bond of maleic and fumaric acids, the isomers of dicarboxylic acids

Functional gel-type resins (OFP) composed of 2-hydroxyethyl methacrylate (HEMA, 20 mol%), styrene (60–77 mol%) and diethylene glycol dimethacrylate, the crosslinking reagent (DEGDMA, 3–20 mol%) are used as supports for palladium catalysts (0.25–2 wt% Pd). The influence of polymer mass expansion on the activity of Pd/OFP catalysts in the hydrogenation of cis- and trans-isomers of unsaturated dicarboxylic acids, maleic (MA) and fumaric (FA), is examined. Starting polymer swells very well in THF and this solvent is used in the hydrogenation experiments. Swelling ability of polymer decreases after insertion of palladium ions due to the crosslinking effect. Reduction of Pd/OFP by NaBH₄ leads to further decrease in swelling ability of polymer caused by the changes in polymer structure observed in FTIR spectroscopy. In the reduced form of the catalysts the nano-particles of Pd (2–3 nm) are formed. Hydrogenation experiments performed in a wide range of operating conditions (Pd loading, catalysts concentration, crosslinking degree of polymer, the size of catalysts grains) show that the swelling of polymer mass during the hydrogenation is a crucial factor for activity of Pd/OFP catalysts. When the catalyst does not swell, the rates of hydrogenation for both isomers are practically the same. They differ only when the catalysts grains are in swollen state. Much higher rate of hydrogenation is observed for MA (the cis-isomer) than for FA (the trans-isomer). This is related to easier penetration of cis-isomer (MA) inside the bulk of the polymer mass which results in more effective utilization of substrates, MA and FA, when present in THF both enhance the expansion of polymer mass but especially cis-isomer, MA. Substrate effect is attributed to the interaction between functional groups present in the reduced catalysts and the hydrogenated reagents, maleic or fumaric acids.     

1,2‐Polymerization of 1,3‐butadiene with Cr(acac)3‐alkylaluminum catalysts

The polymerization of butadiene (Bd) with chromium(III) acetylacetonato [Cr(acac)₃]‐trialkylaluminum (AlR₃) or methylaluminoxane (MAO) catalysts was investigated for the synthesis of 1,2‐poly(Bd). The polymerization of Bd was found to proceed with Cr(acac)₃‐AlR₃ (R‐Me, Et, i‐Bu) catalysts to give poly(Bd) with a high 1,2‐vinyl content, but highly isotactic 1,2‐poly(Bd) was not synthesized. The Cr(acac)₃‐MAO catalyst gave a polymer consisting of low 1,2 units. The effects of the Al/Cr mole ratios on the polymerization of Bd with the Cr(acac)₃‐AlR₃ catalysts were observed. With an increase of Al/Cr mole ratios, the isotactic (mm) content of the polymer increased but the 1,2‐vinyl contents decreased. The effects of the aging time and temperatures of the catalysts on the polymerization of Bd with the Cr(acac)₃‐AlR₃ catalysts were also observed, and the lower polymerization temperature and the prolonged aging time were favored to produce the 1,2‐vinyl structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1621–1627, 2000     

Grafting of Molecularly Ordered Mesoporous Phenylene‐Silica with Molybdenum Carbonyl Complexes: Efficient Heterogeneous Catalysts for the Epoxidation of Olefins

Arenetricarbonyl complexes, or the general formula  C₆H₄Mo(CO)₃ , were incorporated into crystal‐like mesoporous phenylene‐silica by liquid‐phase deposition of molybdenum hexacarbonyl [Mo(CO)₆]. By adjusting the reaction conditions, different molybdenum loadings of 1.5 and 5.9 wt% were obtained, which correspond to 3% and 14% of the phenylene contents. The texture properties of the materials as well as the nature of the surface‐fixed complexes were characterized by powder X‐ray diffraction, transmission electron microscopy (TEM), N₂ adsorption, FT‐IR, UV‐vis and MAS (¹³C, ²⁹Si) NMR spectroscopy. The derivatized organosilicas were examined as catalyst precursors for the liquid‐phase epoxidation of cis‐cyclooctene, 1‐octene, trans‐2‐octene and (R)‐(+)‐limonene at 55 °C, using tert‐butyl hydroperoxide as the oxidant. For each olefin the corresponding epoxide was the only product detected. In the case of cyclooctene, the intrinsic reaction rates per surface molybdenum atom were similar for both Mo loadings (TOF∼1150 mol mol_Mo⁻¹ h⁻¹), suggesting that the resultant materials act as single site epoxidation catalysts. Leaching tests and metal analyses of reaction solutions showed that the catalytic activity stemmed from the immobilized species and not from the leaching of active species into solution. The oxidation of limonene gave limonene oxide as the only product in 95% yield at 3 h, which reveals an outstanding regioselectivity to the epoxidation of the endocyclic double bond.     

Synthesis, Characterization, and Some Properties of 4-Vinylpyridine-Cr(CO)5 Containing Polymers

The polymerization of 4-vinylpyridine (4VP) and 4-vinylpyridine chromium pentacarbonyl [(4VP)Cr(CO)₅] was performed under N₂ atmosphere at 60–80°C temperature range. Different percent of feed (%PF) of Cr(CO)₅ groups were anchored into poly(4-vinylpyridine) (P4VP) by addition of the intermediate Cr(CO)₅THF, which was generated photochemically from Cr(CO)₆ in THF, to the polymer at ambient temperature. The determined percent of anchoring (%PA) has shown that the maximum anchored Cr(CO)₅ groups was 40% (w/w) with respect to P4VP, and the optimum percent of anchoring was 20% (w/w). The rate of polymerization (R _p ) and the activation energy (E _a ) of 4VP in the absence and in the presence of 16.7% Cr(CO)₅(4VP) were determined. Thermal analysis has shown various changes in the properties of the 4VP polymers after modification of the polymer by Cr(CO)₅ groups. The X-ray diffraction and the melting enthalpy derived from the DSC thermogram revealed that the synthesized poly[(CO)₅Cr(4VP)] has a crystallinity of about 40%, whereas no crystallinity was observed for pure P4VP.     

Influence of imine‐carbon substituent in 6‐bromo‐2‐iminopyridine‐based cobalt(II) complexes on 1,3‐butadiene polymerization

6‐Bromo‐2‐iminopyridine cobalt(II) complexes bearing different imine‐carbon substituents ( Co1 – Co7 ) were synthesized and subsequently employed for 1,3‐butadiene polymerization. All the complexes were identified using Fourier transform infrared spectra and elemental analysis, and complexes Co1 and Co3 were further characterized using single‐crystal X‐ray diffraction analysis, demonstrating they adopted distorted trigonal bipyramidal and tetrahedral geometries, respectively. Activated by methylaluminoxane, these complexes exhibited high cis‐1,4 selectivity, and the activity was highly dependent on the substituent at the imine‐carbon position of the ligand. Addition of PPh₃ to the polymerization systems could enhance the catalytic activity and simultaneously switched the selectivity from cis‐1,4 to cis‐1,2 manner. On the basis of the obtained results, a plausible mechanism involving the regulation of selectivity and activity is proposed. © 2019 Society of Chemical Industry     

Hydrogenation of canola oil using chromium catalysts

Homogeneous, supported and precipitated chromium catalysts were prepared from chromium hexacarbonyl in an attempt to selectively hydrogenate canola oil. These chromium compounds showed low activity, lowering the iodine value of the oil by only 10 IV units. The concentration oftrans-isomers, however, was very low (<1% for most runs). Infrared spectroscopy revealed the presence of a Cr(CO)₃(diene) PPH₃ complex in two of the hydrogenated oils. The selectivity and the mechanism by which chromium catalysts hydrogenate unsaturates are discussed.     

SHS-produced β-sialons as supports for oxidation catalysts

SHS-produced β-sialons Si_6−z Al _z O _z N_8−z (z = 1, 3, 4) were tested as supports for oxidation catalysts comprising of unary, binary or ternary mixtures of transition metal (Cr, Mn, Fe, Co, Ni, Cu) oxides and also KMnO₄ and K₂Cr₂O₇. In oxidation of CO and propane (C₃H₈), the highest activity was exhibited by the catalysts based on cobalt oxides. Suggested are some methods for activation of the above catalysts.      

Preparation of supported gold catalysts from gold complexes and their catalytic activities for CO oxidation

A phosphine-stabilized mononuclear gold complex Au(PPh₃)(NO₃) (1) and a phosphine-stabilized gold cluster [Aug(PPh₃)₈](NO₃)₃ (2) were used as precursors for preparation of supported gold catalysts. Both complexes 1 and 2 supported on inorganic oxides such as -Fe₂O₃, TiO₂, and SiO₂ were inactive for CO oxidation, whereas the 1 or 2/ oxides treated under air or CO or 5% h₂/Ar atmosphere were found to be active for CO oxidation. The catalytic activity depended on not only the treatment conditions but also the kinds of the precursor and the supports used. The catalysts derived from 1 showed higher activity than those derived from 2. -Fe₂O₃ and TiO₂ were much more efficient supports than SiO₂ for the gold particles which were characterized by XRD and EXAFS.     

Butadiene polymerisation using ternary neodymium-based catalyst systems

Summary Ternary catalyst systems for the polymerisation of 1,3-butadiene to high cis content were studied. The systems Nd(carboxylate)₃/tert-butyl X /diisobutyl aluminium hydride (carboxylate=naphthenate, versatate; X=Cl, Br, I) were studied with respect to the halide:Nd ratio and halide type on catalyst activity and polymer characteristics. A lowering of the halide:Nd ratio results in lower conversions to polymer and a change in polymer molecular weight distribution. Catalyst stability is affected by halide type; instability, or tendency to precipitate, following the order I>Br>Cl. Less active catalysts (e.g. based on tert-butyl iodide) give low conversions and broad polymer MWD. Cis content remains at 98% and is unaffected by a lowering of halide:Nd ratio or a change in halide type.     

Polymerization of 1,3-butadiene using aluminoxane-based Nd-carboxylate catalysts

The ternary neodymium-based catalyst for the polymerization of 1,3-butadiene, Nd(versatate)₃/AliBu₂H/tert-butyl chloride, has been examined with respect to the effects of replacing the alkylaluminium hydride with aluminoxane, namely methylaluminoxane (MAO) and tetraisobutyldialuminoxane (TIBAO). Catalysts based on MAO were found to be active even in the absence of a halogen source, whereas TIBAO catalysts were active only when a halogen was present (catalyst activity TIBAO > MAO). Using catalysts prepared both preformed and in situ, the effects of polymerization temperature, solvent and MAO level on catalyst activity and the characteristics of the final polymer are discussed. Polybutadiene cis contents and molecular weights were higher with MAO-based catalysts than with AliBu₂H-based catalysts. Cis contents were also higher when MAO catalysts containing tert-butyl chloride were used, compared to their non-chloride counterparts.     

Butadiene polymerisation using ternary neodymium-based catalyst systems

Summary Ternary catalyst systems for the polymerisation of 1,3-butadiene to high cis content were studied. The systems Nd(carboxylate)₃/tert-butyl chloride/diisobutylaluminium hydride (carboxylate = naphthenate, versatate) were studied with respect to the order of catalyst component addition on catalyst activity and polymer characteristics. Stable catalysts which give relatively narrow molecular weight distribution are give by component addition order Nd(carboxylate)₃+diisobutylaluminium hydride+tert-butyl chloride. Less stable systems giving broader polymer molecular weight distributions are given by addition orders tert-butyl chloride+diisobutylaluminium hydride+Nd(carboxylate)₃ and Nd(carboxylate)₃ +tert-butyl chloride+diisobutylaluminium hydride.     

Nanodispersed Au/Al2O3 catalysts for low-temperature CO oxidation: Results of research activity at the Boreskov Institute of Catalysis

This paper presents some important results of the studies on preparation and catalytic properties of nanodispersed Au/Al₂O₃ catalysts for low-temperature CO oxidation, which are carried out at the Boreskov Institute of Catalysis (BIC) starting from 2001. The catalysts with a gold loading of 1–2 wt.% were prepared via deposition of Au complexes onto different aluminas by means of various techniques (“deposition-precipitation” (DP), incipient wetness, “chemical liquid-phase grafting” (CLPG), chemical vapor deposition (CVD)). These catalysts have been characterized comparatively by a number of physical methods (XRD, TEM, diffuse reflectance UV/vis and XPS) and catalytically tested for combustion of CO impurity (1%) in wet air stream at near-ambient temperature. Using the hydroxide or chloride gold complexes capable of chemical interaction with the surface groups of alumina as the catalyst precursors (DP and incipient wetness techniques, respectively) produces the catalysts that contain metallic Au particles mainly of 2–4 nm in diameter, uniformly distributed between the external and internal surfaces of the support granules together with the surface “ionic” Au oxide species. Application of organogold precursors gives the supported Au catalysts of egg shell type which are either close by mean Au particle size to what we obtain by DP and incipient wetness techniques (CVD of (CH₃)₂Au(acac) vapor on highly dehydrated Al₂O₃ in a rotating reactor under static conditions) or contain Au crystallites of no less than 7 nm in size (CLPG method). Regardless of deposition technique, only the Cl-free Au/Al₂O₃ catalysts containing the small Au particles (d_i ≤ 5 nm) reveal the high catalytic activity toward CO oxidation under near-ambient conditions, the catalyst stability being provided by adding the water vapor into the reaction feed. The results of testing of the nanodispersed Au/Al₂O₃ catalysts under conditions which simulate in part removal of CO from ambient air or diesel exhaust are discussed in comparison with the data obtained for the commercial Pd and Pt catalysts under the same conditions.     

Preparation of shish‐kebab and nanofiber polyethylene with chromium/Santa Barbara amorphous silica‐15 catalysts

Cr/SBA‐15 catalysts were prepared by the grafting of chromium nitrate nonahydrate [Cr(NO₃)₃·9H₂O] complexes onto SBA‐15 mesoporous materials. Shish‐kebab and nanofiber polyethylenes (PEs) were prepared under different temperatures via ethylene extrusion polymerization with the Cr(NO₃)₃·9H₂O catalytic system. The diameter of a single nanofiber was 100–250 nm. Scanning electron microscopy images showed that the polymer obtained from the SBA‐15‐supported catalyst under different polymerization temperatures produced nanofiber and/or shish‐kebab morphologies. X‐ray diffraction and differential scanning calorimetry were used to characterize microstructures of the materials. Polymers obtained with all of the catalysts showed a melting temperature, bulk density, and high load melt index; this indicated the formation of linear high‐density PE. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hydrogenation of dienes with cationic rhodium complexes

Methylcis-9,cis-12-octadecadienoate (methyl linoleate;c9,c12), itst10,t12 andt10,c12 isomers and methylcis-9-octadecenoate (methyl oleate;c9) were hydrogenated with rhodium complexes, the active species of which consisted of [RhL₂]⁺ and [RhL₂H₂]⁺ with ligands L=P(C₂H₅)₂C₆H₅ (catalyst A) P(i-C₄H₉)₃ (catalyst B) and P(CH₃)₃ (catalyst C). Using these catalysts the influence of steric effects on the reaction mechanism of hydrogenation of dienes was studied. The reactions were carried out in 2-propanol at atmospheric hydrogen pressure and ambient temperature. During hydrogenation ofc9 on catalysts A and B, geometrical isomerization mainly occurred, whereas on catalyst C some positional isomerization also took place.C9,c12 was almost exclusively hydrogenated via conjugated intermediates on catalyst A. On catalyst C, one of the double bonds was hydrogenated directly, in most cases. In the absence of hydrogen, catalysts A and B conjugatedc9,c12 very fast. The conjugation activity of catalyst C was much lower. Catalyst C showed a high 1,5-shift activity for the conjugatedcis, trans andtrans, cis intermediates during hydrogenation, in contrast to catalysts A and B, which showed a poor activity in this respect.T10,t12 was hydrogenated almost exclusively via 1,4-addition of hydrogen to thecisoid conformation, whereas only a slight preference was found in this mechanism over 1,2-addition for the hydrogenation oft10,c12. On the sterically unhindered catalysts A and C thetrans double bond int10,c12 was preferentially hydrogenated whereas on catalyst B, with its bulky ligands, thecis double bond was reduced faster than thetrans double bond.