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Крон, Т. Е.; Terekhova, M. I.; Noskov, Yu. G.; Петров, Е. С.

doi:10.1023/a:1010453015217

Cited by 22 publications

(22 citation statements)

References 10 publications

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“…The rates of formation of the acids increased as the carbon monoxide pressure was increased and as the water concentration was increased up to [H 2 O] = 2 M . The same mechanism as that for styrene was suggested (Scheme ) 107.…”

Section: Studies Of the Mechanism Of Palladium‐catalysed Carbonylationssupporting

confidence: 54%

“…Kinetic and spectroscopic data were used to explain the effect of SnCl 2 . It was proposed that it involves the displacement of CO ligands from Pd II ‐containing intermediates by the π‐acceptor SnCl 3 − , and leads to a higher concentration of phosphane hydride complexes that selectively afford the linear acid (Scheme ) 107.…”

Section: Studies Of the Mechanism Of Palladium‐catalysed Carbonylationsmentioning

confidence: 99%

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On the Mechanism of the Hydroxycarbonylation of Styrene with Palladium Systems

Rı́o

Claver

Leeuwen³

2001

Eur. J. Inorg. Chem.

116

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We present a review concerning the mechanism involved in the hydroxycarbonylation of styrene. We discuss the intermediates proposed in the literature, the effect of the acidic medium, the reactivity and kinetics, as well as the results of theoretical calculations on hydroxycarbonylation and related reactions. We have performed an in situ high-pressure NMR [a] Inmaculada del Río (left) received her Ph.D. in 2000 from the University Rovira i Virgili working on mechanistic aspects of hydroformylation and hydroxycarbonylation reactions. Carmen Claver (right) is Professor of Inorganic Chemistry at the University Rovira i Virgili in Tarragona (Spain), a position she has held since 1991. She received her Ph.D. in 1978 from the University of Zaragoza (Spain) working in the field of organometallic chemistry with Prof. Luis A. Oro. Her present research is focused on fundamental aspects of homogeneous catalysis with transition metals, especially in asymmetric catalysis. Piet W. N. M. van Leeuwen is Professor of Homogeneous Catalysis at the University of Amsterdam, a position he has held since 1989. He has spent much of his career at Shell Research in Amsterdam working in the area of homogeneous catalysis and organometallic chemistry. His present research is aimed at the development of novel transition metal homogeneous catalysts, using the full range of available tools and techniques.MICROREVIEWS: This feature introduces the readers to the authors' research through a concise overview of the selected topic. Reference to important work from others in the field is included.2719 study to obtain more insight into the mechanisms that control the regioselectivity and have assessed how this is affected by the phosphorus ligand and the catalyst precursor. We observed palladium hydride and palladium acyl species and we suggest a catalytic cycle involving palladium hydride, palladium alkyl, and palladium acyl intermediates.

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Section: Studies Of the Mechanism Of Palladium‐catalysed Carbonylationssupporting

confidence: 54%

Section: Studies Of the Mechanism Of Palladium‐catalysed Carbonylationsmentioning

confidence: 99%

On the Mechanism of the Hydroxycarbonylation of Styrene with Palladium Systems

Rı́o

Claver

Leeuwen³

2001

Eur. J. Inorg. Chem.

116

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“…Reppe carbonylation combines three reactants: an unsaturated hydrocarbon substrate, a carbonyl source, and a nucleophile (eqs 8−10). The most frequently studied hydrocarbon substrates are alkenes, ,− alkynes, − conjugated dienes (typically butadiene), − and aryl-substituted alkenes, most often styrene. − The aryl-substituted alkenes are treated separately from alkenes because of their special application and selectivity pattern (vide infra).…”

Section: Chemistry and Productsmentioning

confidence: 99%

Palladium-Catalyzed Reppe Carbonylation

2001

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PdX2L2/L/HA (A = weakly coordinating anion, L = phosphine) complexes are active catalysts in the hydroesterification of alkenes, alkynes, and conjugated dienes. Shell, the only major corporate player in the field, recently developed two very active catalyst systems tailored to the hydroesterification of either alkenes or alkynes. The hydroesterification of propyne with their Pd(OAc)2/PN/HA (PN = (2-pyridyl)diphenylphosphine, HA = strong acid with weakly coordinating anion, like methanesulfonic acid) catalyst has been declared commercially ready. However, despite the significant progress in the activity of Pd-hydroesterification catalysts, further improvements are warranted. Thus, for example, activity maintenance still seems to be an issue. Homogeneous Pd catalysts are prone to a number of deactivation reactions. Activity and stability promoters are often corrosive and add to the complexity of the system, making it less attractive. Nonetheless, the versatility of the process and its tolerance toward the functional groups of substrates should appeal especially to the makers of specialty products. Although hydroesterification yields esters from alkenes, alkynes, and dienes in fewer steps than hydroformylation does, the latter has some advantages at the current state of the art. (1) Hydroformylation catalysts, particularly some recently published phosphine-modified Rh systems, can achieve very high regioselectivity for the linear product that hydroesterification catalysts cannot match yet. By analogy with hydroformylation, bulkier ligands ought to be tested in hydroesterification to increase normal-ester selectivity. (2) Hydroformylation is proven, commercial. Hydroesterification can only replace it if it can provide significant economic incentives. Similar or just marginally better performance could not justify the cost of development of a new technology. (3) Hydroesterification requires pure CO while hydroformylation uses syngas, a mixture of CO and H2. The latter is typically more available and less expensive (for industrial applications CO is most often separated from syngas). (4) The acid component of the hydroesterification catalyst makes the process corrosive. It would be desirable to develop new hydroesterification catalysts that do not require acid stabilizer/activity booster. Clearly, any new hydroesterification technology will directly compete with the hydroformylation route. This is especially true for olefin feeds, since both processes add one CO to the olefin, yielding oxygenates that can be converted into identical products. For some niche applications, like the production of MMA from propyne, hydroesterification seems to have an advantage as compared to hydroformylation due to the high activity and selectivity of the Pd(OAc)2/(2-pyridyl)diphenylphosphine catalyst. Since hydroesterification is an emerging technology, it is reasonable to assume that the potential for improvement is greater than in the mature hydroformylation. It is therefore possible that hydroesterification will become competitive in ...

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“…Currently, data are available on the synthesis of linear and branched esters by the hydrocarboalkoxylation of alkenes, cycloalkenes, styrene, and phenylacetylene [1][2][3][4][5][6]. However, some issues concerning the mechanism of these reactions still remain open.…”

Section: Introductionmentioning

confidence: 99%

Kinetic aspects of the influence of concentrations of methanol and the trans-2,3-bis(diphenylphosphinomethyl)norbornane promoting additive on the hydrocarbomethoxylation of cyclohexene catalyzed by the Pd(OAc)2/p-toluenesulfonic acid system

Nifant’ev

Sevostyanova

Баташев

et al. 2015

Reac Kinet Mech Cat

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The effects of temperature, the concentrations of methanol and the trans-2,3-bis(diphenylphosphinomethyl)norbornane (TBDPN) promoting additive on the rate of cyclohexene hydrocarbomethoxylation catalyzed by the Pd(OAc) 2 /ptoluenesulfonic acid system were studied. It was found that in the 358-383 K temperature range, the increase in the CH 3 OH concentration from 0 to 0.15 mol/L induces a virtually linear increase in the reaction rate, which slows down as the methanol concentration further increases. In the temperature range of 343-373 K, the dependences of the reaction rate on the TBDPN concentration pass through maxima at [TBDPN] = (3.0-4.0) 9 10 -3 mol/L. The results were interpreted in terms of the hydride mechanism that included diphosphinepalladium complexes as intermediates and was supplemented by ligand exchange reactions, resulting in a decrease in the activity of the palladium catalyst. The effective constants of the previously derived kinetic equation in the temperature range of 343-383 K were estimated by the least-squares method. The effective activation energies were determined and used to evaluate the enthalpy change in the ligand exchange reaction between the complexes Pd(TBDPN) 3 and [HPd(TBDPN)(CH 3 OH)]OTs. The zerovalent complex Pd(TBDPN) 3 was concluded to be more stable than the hydride complex [HPd(TBDPN)(CH 3 OH)]OTs.

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Cited by 22 publications

References 10 publications

On the Mechanism of the Hydroxycarbonylation of Styrene with Palladium Systems

On the Mechanism of the Hydroxycarbonylation of Styrene with Palladium Systems

Palladium-Catalyzed Reppe Carbonylation

Kinetic aspects of the influence of concentrations of methanol and the trans-2,3-bis(diphenylphosphinomethyl)norbornane promoting additive on the hydrocarbomethoxylation of cyclohexene catalyzed by the Pd(OAc)2/p-toluenesulfonic acid system

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