Synthesis and spectroscopic characterisation of all the intermediates in the Pd-catalysed methoxycarbonylation of ethene

Eastham, Graham R.; Heaton, Brian T.; Iggo, Jonathan A.; Tooze, Robert P.; Whyman, Robin; Zacchini, Stefano

doi:10.1039/b001110j

Cited by 134 publications

(91 citation statements)

References 6 publications

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“…Thus, Heaton and co-workers were the first to isolate all the intermediates involved in the methoxycarbonylation of ethylene. 130 The authors found that, contrary to what was previously suggested, the palladium-hydride species was stable in the presence of oxygen at temperatures as high as 80℃ or in the presence of an excess of benzoquinone. No evidence of the palladium-methoxy complex was found.…”

Section: Alkoxycarbonylationmentioning

confidence: 71%

Polymer precursors from catalytic reactions of natural oils

et al. 2012

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Dimethyl 1,19-nonadecanedioate is produced from the methoxycarbonylation of commercial olive, rapeseed or sunflower oils in the presence of a catalyst derived from [Pd 2 (dba) 3 ], bis(ditertiarybutylphosphinomethyl)benzene (BDTBPMB) and methanesulphonic acid (MSA). The diester is then hydrogenated to 1,19-nonadecanediol using Ru/1,1,1-tris-(diphenylphosphinemethyl)ethane (triphos). 1,19-Nonadecadienoic acid is hydrogenated to short chain oligoesters, which can themselves be hydrogenated to 1,19-nonadecanol by hydrogenation in the presence of water.

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Section: Alkoxycarbonylationmentioning

confidence: 71%

Polymer precursors from catalytic reactions of natural oils

et al. 2012

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“…C 3 -bridged diphenylphosphine of the type reported on the title, or other diaryl analogues, for example with ortho-methoxy substituents on the phenyl rings, are highly active in the copolymerization process [17], whereas bulkier diphosphines such as t-BuP(CH 2 ) 3 PBu-t or 1,2-bis[(di-tertbutyl)phosphinomethyl]benzene are very active and selective in promoting the methoxycarbonylation to MP [8][9][10][11]17]. That steric bulk plays a role of paramount importance in controlling the selectivity of the reaction is also well illustrated by the results obtained using cationic Pd(II) complexes of 1,1 0 -bis(dialkylphosphino) ferrocene ligand, as when alkyl = methyl the catalyst is very active in promoting high molecular weight PK, whereas when alkyl = ethyl lower molecular weight PK are obtained, and when alkyl = i-propyl the products are MP and DEK [18].…”

Section: Introductionmentioning

confidence: 99%

“…Monocarbonylated products form through the so called ''hydride'' mechanism, which involves the insertion of the olefin into a Pd-H bond with formation of a Pd-alkyl bond, followed by the insertion of CO into the Pd-alkyl intermediate with formation of a Pd-acyl species, which undergoes alcoholysis or hydrolysis to the ester or the acid with reformation of the Pd-H species starting the catalytic cycle [8][9][10][11]. DEK forms when the insertion of a second molecule of ethene into the Pd-acyl bond occurs with formation of a Pd-alkylacyl intermediate, followed by protonolysis [12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and X-ray structure of [Pd(SO4)(dppp)]·H2O, a catalyst for the CO-ethene copolymerization [dppp=1,3-bis(diphenylphosphino)propane]

Cavinato

Vavasori

Toniolo

et al. 2005

Inorganica Chimica Acta

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The title complex has been synthesized by first reacting dppp with Pd(AcO) 2 in acetone and then with NaHSO 4 in water. It has been characterized by IR, NMR and X-ray diffraction studies. The 31 P NMR spectrum in DMSO shows a singlet at 16.62 ppm indicating that the two P atoms are equivalent and that the sulfate anion is weakly coordinating. The X-ray structure shows that the Pd atom is surrounded in an almost regular square planar environment by the two P atoms and by two O atoms of the sulfate anion and that the neutral complex is accompanied by a water molecule of crystallization. The Pd-P distances (2.217(1) and 2.233(1)) and the P-Pd-P angle (90.78(3)°) are close to those found in other complexes where the chelating diphosphine is the same. Also the Pd-O distances and the O-Pd-O bond angle are comparable to those of other relevant chelating ligands.In MeOH, the title complex, in combination with H 2 SO 4 , catalyses the CO-ethene copolymerization. The productivity reaches a maximum upon increasing the H 2 SO 4 /Pd ratio up to ca. 470 (7650 g of polyketone/g Pd h at 90°C and 45 atm, CO/ethene 1/1). The viscosity of the polyketone passes through a maximum of 0.95 dL/g in m-cresol when the above ratio is ca. 100. It has been proposed that acid promotes the copolymerization process by destabilizing the b-and c-chelates intermediates involved in chain growing process, thus favoring the insertion of the monomers. At relatively high acid concentration the lowering of productivity and viscosity suggests that the sulfate anion competes with the monomers for the coordination to the metal center.In H 2 O-CH 3 COOH as a solvent the productivity strongly depends on the H 2 O/CH 3 COOH ratio, as it passes through a maximum of 12 000 g polymer/g Pd h in the presence of ca. 60% of H 2 O. The productivity is significantly lower than that found when the acetate and chloride analogues are used (27 000 g polyketone/g Pd AE h). Thus, it is likely that the sulfate anion assists significantly the copolymerization process even though the concentration of CH 3 COOH/CH 3 COO À is much preponderant.

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“…However, more interesting direction in practice is the producing ethene from ethanol over Fe-ZSM-5 or carbon-based catalyst, since ethene is considered as more valuable than ethanol [221,222]. Ethene can be converted also to methyl propanoate via methoxycarbonylation over a palladium catalyst [223]. Methyl propionate is used as a solvent for cellulose nitrate and as a raw material in the production of paints and varnishes [224].…”

Section: Potential Existing Technologies and New Considerations For Vmentioning

confidence: 99%

Utilization of Volatile Organic Compounds as an Alternative for Destructive Abatement

et al. 2015

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Abstract:The treatment of volatile organic compounds (VOC) emissions is a necessity of today. The catalytic treatment has already proven to be environmentally and economically sound technology for the total oxidation of the VOCs. However, in certain cases, it may also become economical to utilize these emissions in some profitable way. Currently, the most common way to utilize the VOC emissions is their use in energy production. However, interesting possibilities are arising from the usage of VOCs in hydrogen and syngas production. Production of chemicals from VOC emissions is still mainly at the research stage. However, few commercial examples exist. This review will summarize the commercially existing VOC utilization possibilities, present the utilization applications that are in the research stage and introduce some novel ideas related to the catalytic utilization possibilities of the VOC emissions. In general, there exist a vast number of possibilities for VOC OPEN ACCESSCatalysts 2015, 5 1093 utilization via different catalytic processes, which creates also a good research potential for the future.

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Synthesis and spectroscopic characterisation of all the intermediates in the Pd-catalysed methoxycarbonylation of ethene

Cited by 134 publications

References 6 publications

Polymer precursors from catalytic reactions of natural oils

Polymer precursors from catalytic reactions of natural oils

Synthesis, characterization and X-ray structure of [Pd(SO4)(dppp)]·H2O, a catalyst for the CO-ethene copolymerization [dppp=1,3-bis(diphenylphosphino)propane]

Utilization of Volatile Organic Compounds as an Alternative for Destructive Abatement

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