Carbonylation of olefins by carbon monoxide and alcohols in the presence of Pd-complex catalytic system

In order to develop new, efficient and environmentally friendly methods for the preparation of practically valuable esters of carboxylic acids, studies of the hydroalkoxycarbonylation reaction of a number of terminal olefins of normal structure (hexene-1, heptene-1, octene-1, nonene-1) with carbon monoxide and alcohols in presence of metal complex catalysts based on palladium phosphine complexes at low carbon monoxide pressures (≤ 20 atm).Two-and three-component systems based on PdCl2 and Pd(Acac)2, PdCl2(PPh3)2, Pd(PPh3)4 complexes containing a free ligand (PPh3) as a stabilizer and Bronsted acid (TsOH) as a promoter were studied as catalysts. It was shown that only the three-component systems PdCl2-PPh3-TsOH, PdCl2(PPh3)2-PPh3-TsOH, Pd(Acac)2-PPh3-TsOH, and Pd(PPh3)2-PPh3-TsOH have the highest catalytic activity in the studied reactions. It was found that the reaction of hydroalkoxycarbonylation of α-olefins proceeds with the formation of a mixture of linear and branched products. The influence of various conditions of the reaction (the ratio of the initial reagents and the components of the catalytic systems, temperature, CO pressure, duration) on the course of the process and on the yield of the target products was investigated. The optimal parameters of the studied reactions have been found.

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Palladium Promoted Copolymerization of Carbon Monoxide with Polar or Nonpolar Olefinic Monomers

Current Organic Chemistry ◽

10.2174/1385272824999201102221113 ◽

2020 ◽

Vol 24 ◽

Author(s):

Yanlin Zong ◽

Qiankun Li ◽

Hongliang Mu ◽

Zhongbao Jian

Keyword(s):

Carbon Monoxide ◽

Physical Properties ◽

Vinyl Monomers ◽

Pd Catalysts ◽

Catalytic Systems

Abstract:: The copolymers of carbon monoxide (CO) and olefins, namely polyketones, are a family of widely used materi-als. In the catalytic preparation of these materials, palladium(II) catalysts represent the most successful catalytic systems. The production of both alternating and non-alternating polyketones has been achieved, with great difference in their physical properties. Herein, a variety of palladium(II) catalysts employed for the copolymerization of CO with various olefinic mon-omers such as ethylene, α-olefins, styrene and polar vinyl monomers are fully summarized. The influence of important fac-tors such as solvents and counterions on specific copolymerization, is also discussed. This review aims to enlighten the de-sign of new Pd catalysts with improved properties, as well as the development of new polyketone materials.

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Low-Carbon Monoxide Hydrogen by Sorption-Enhanced Reaction

International Journal of Chemical Reactor Engineering ◽

10.2202/1542-6580.1055 ◽

2003 ◽

Vol 1 (1) ◽

Cited By ~ 8

Author(s):

Douglas P Harrison ◽

Zhiyong Peng

Keyword(s):

Carbon Dioxide ◽

Carbon Monoxide ◽

Hydrogen Production ◽

Proton Exchange Membrane ◽

Primary Energy ◽

Proton Exchange ◽

Raw Material ◽

Impurity Level ◽

Low Carbon ◽

Enhanced Production

Hydrogen is an increasingly important chemical raw material and a probable future primary energy carrier. In many current and anticipated applications the carbon monoxide impurity level must be reduced to low-ppmv levels to avoid poisoning catalysts in downstream processes. Methanation is currently used to remove carbon monoxide in petroleum refining operations while preferential oxidation (PROX) is being developed for carbon monoxide control in fuel cells. Both approaches add an additional step to the multi-step hydrogen production process, and both inevitably result in hydrogen loss. The sorption enhanced process for hydrogen production, in which steam-methane reforming, water-gas shift, and carbon dioxide removal reactions occur simultaneously in the presence of a nickel-based reforming catalyst and a calcium-based carbon dioxide sorbent, is capable of producing high purity hydrogen containing minimal carbon monoxide in a single processing step. The process also has the potential for producing pure CO2 that is suitable for subsequent use or sequestration during the sorbent regeneration step. The current research on sorption-enhanced production of low-carbon monoxide hydrogen is an extension of previous research in this laboratory that proved the feasibility of producing 95+% hydrogen (dry basis), but without concern for the carbon monoxide concentration. This paper describes sorption-enhanced reaction conditions temperature, feed gas composition, and volumetric feed rate required to produce 95+% hydrogen containing low carbon monoxide concentrations suitable for direct use in, for example, a proton exchange membrane fuel cell.

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Ruthenium complexes containing Group 5B donor ligands. Part 8. Reactions of binuclear carbonyl- and thiocarbonyl-ruthenium(II) triphenylphosphine complexes with alkoxy(phenyl)phosphines and of mononuclear ruthenium(II) alkoxy(phenyl)phosphine complexes with carbon monoxide

Journal of the Chemical Society Dalton Transactions ◽

10.1039/dt9790001045 ◽

1979 ◽

pp. 1045 ◽

Cited By ~ 5

Author(s):

Wilma J. Sime ◽

T. Anthony Stephenson

Keyword(s):

Carbon Monoxide ◽

Ruthenium Complexes ◽

Donor Ligands ◽

Phosphine Complexes

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Reductive formylation of aromatic halides under low carbon monoxide pressure catalyzed by transition-metal compounds

The Journal of Organic Chemistry ◽

10.1021/jo00195a026 ◽

1984 ◽

Vol 49 (21) ◽

pp. 4009-4011 ◽

Cited By ~ 74

Author(s):

I. Pri-Bar ◽

O. Buchman

Keyword(s):

Carbon Monoxide ◽

Transition Metal ◽

Transition Metal Compounds ◽

Low Carbon ◽

Metal Compounds

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Methanol carbonylation to acetaldehyde on Au particles supported by single-layer MoS2 grown on silica

Journal of Physics Condensed Matter ◽

10.1088/1361-648x/ac40ad ◽

2021 ◽

Vol 34 (10) ◽

pp. 104005

Author(s):

Kortney Almeida ◽

Katerina Chagoya ◽

Alan Felix ◽

Tao Jiang ◽

Duy Le ◽

...

Keyword(s):

Carbon Monoxide ◽

Density Functional ◽

Ostwald Ripening ◽

Reaction Pathway ◽

Single Layer ◽

Process Conditions ◽

Higher Alcohols ◽

Low Carbon ◽

Functional Theory ◽

Supported Gold

Abstract Homogenous single-layer MoS2 films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS2 films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2 surface. A gas mixture of carbon monoxide (CO) and methanol (CH3OH) was partially converted to acetaldehyde (CH3CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C2 species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS2 facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. The formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.

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An Artifact in the Analysis of Oxygenated Blood for Its Low Carbon Monoxide Content

Clinical Chemistry ◽

10.1093/clinchem/16.11.896 ◽

1970 ◽

Vol 16 (11) ◽

pp. 896-899 ◽

Cited By ~ 23

Author(s):

F Lee Rodkey ◽

Harold A Collison

Keyword(s):

Carbon Monoxide ◽

Citric Acid ◽

Chromatographic Method ◽

Low Carbon ◽

Rate Of Reaction ◽

Gas Chromatographic Method ◽

Carbon Monoxide Content

Abstract A sensitive gas chromatographic method for blood CO determination was used to analyze samples of reduced and oxygenated blood having identical low CO content. Oxygenated blood always released more CO than did the reduced samples when neutral ferricyanide was used as oxidant. Several reagents for CO release from blood were applied to both oxygenated and reduced samples. CO release by K3Fe(CN)6 from oxygen-free blood or COHb solutions was complete and constant from pH 1.5 to 6. Values of extra CO released from oxygenated samples varied from 0.003 vol % at pH 1.5 to over 0.015 vol % at pH 6. The least amounts of excess CO were produced between pH 2 and 4.5. Neutral K2Cr2O7 causes less excess CO formation than does K3Fe(CN)6, but the rate of reaction with COHb is low. Neutral KMnO4 and acid K2Cr2O7 cause extreme formation of excess CO from blood in amounts many times the amount of COHb present. Acid KIO3 effectively releases CO from COHb solutions and reduced blood, but causes more excess CO formation from oxygenated blood than K3Fe(CN)6. When CO is released in citric acid with K3Fe(CN)6 at a pH of about 3.5, the CO released from oxygenated blood is only about 0.001 vol % greater than that released from reduced samples. These differences indicate formation of small amounts of CO during reactions used to release CO from blood. Reduced hemoglobin and carboxyhemoglobin appear to be much more stable to these procedures than is oxyhemoglobin.

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