The mechanism of the phosphine-modified nickel-catalyzed acetic acid process

Moser, William R.; Marshik-Guerts, Barbara; Okrasinski, Stanley J.

doi:10.1016/s1381-1169(98)00369-0

Cited by 27 publications

(19 citation statements)

References 16 publications

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“…In the present study, reactions of cobalt acyl complexes [Co(CO) 3 (L)(COR)] with hydrogen were monitored by in situ high-pressure IR spectroscopy using a cylindrical internal reflectance (CIR) cell of the type developed by Moser. − Reactions were carried out using toluene as solvent at temperatures up to ∼70 °C and H 2 pressures up to ∼20 bar. A typical set of IR spectra, for the reaction of [Co(CO) 3 (PEtPh 2 )(COMe)] with H 2 at 52 °C is shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…Reactions of [Co(CO) 3 (L)(COR)] with hydrogen were monitored in situ by high-pressure IR spectroscopy using a cylindrical internal reflectance (CIR) cell comprising an autoclave (Parr) modified (by SpectraTech) to accommodate a crystalline silicon CIR rod, as described by Moser. − Spectra were recorded using a Perkin-Elmer Spectrum GX FTIR spectrometer fitted with an MCT detector. The cell was placed directly in the spectrometer sample compartment and aligned to maximize IR energy throughput using a tilt table.…”

Section: Methodsmentioning

confidence: 99%

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Ligand Effects on Reactivity of Cobalt Acyl Complexes

et al. 2012

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Hydrogenolysis reactions of cobalt acyl complexes, [Co(CO)3(L)(COR)] (L = phosphine, R = Me, n Pr) have been monitored using in situ IR spectroscopy at moderate temperatures (<75 °C) and pressures (<25 bar). The reactions provide a model for the product-formation step in phosphine-modified, cobalt-catalyzed hydroformylation. The reaction kinetics are dependent on L, with the fastest rate being observed for the complex containing n-pentyl-9-phosphabicyclo[4.2.1]nonane (a 5-PhobPC5). The observed dependence of rate on H2 and CO pressure is consistent with a mechanism involving initial CO dissociation, followed by reaction of [Co(CO)2(L)(COR)] with H2. Isotopic exchange experiments, monitored by IR spectroscopy, demonstrate that both terminal and acetyl carbonyls of [Co(CO)3(L)(COR)] exchange with free 13CO. Kinetic data are also reported for reactions of [Co(CO)3(L)(COR)] with triphenyltinhydride. A zero-order dependence on [Ph3SnH] (at large excess) and positive values of ΔS ‡ demonstrate rate-determining CO dissociation. For a series of less bulky, symmetrical phosphines, the rates follow the sequence PEt3 < PMe2Ph ∼ PEtPh2 < PPh3 < P(4-ClC6H4)3, in accord with their electron-donating strength. Higher rates are found for more bulky phosphines, and the fastest rate is again found for L = a 5-PhobPC5. Calculations using density functional theory indicate that the CO dissociation energy for [Co(CO)3(L)(COMe)] is influenced by the stereoelectronic properties of L, with steric bulk having a substantial effect. X-ray crystal structures are reported for [Co(CO)3(PEtPh2)(COMe)], [Co(CO)3(s-PhobPC5)]2, and [Co(CO)3(a 5-PhobPC5)]2.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Ligand Effects on Reactivity of Cobalt Acyl Complexes

et al. 2012

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“…In this work, the carboxyl was generated by the reaction COO - + H →COOH - . The acids then were obtained by the following reactions: Another reaction route via CO is similar to the catalytic route . For example, the formation of acetic acid via the CO route can be expressed by the following reactions: or The aforementioned analysis shows that the C atom of the carboxyl comes from CO 2 or CO, which is the dissociated product of CO 2 .…”

Section: Resultsmentioning

confidence: 99%

Density Functional Theory Study of Synthesis of Oxygenates and Higher Hydrocarbons from Methane and Carbon Dioxide Using Cold Plasmas

2003

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A density functional theory (DFT) study has been conducted in this work to investigate the reaction mechanism of synthesis of oxygenates and higher hydrocarbons from methane (CH 4 ) and carbon dioxide (CO 2 ), using cold plasmas. The main dissociation routes of the reactants were analyzed. The feasibility of the formation of various products, including syngas, higher hydrocarbons, and oxygenates, was discussed. The DFT study confirmed that the major obstacle of the synthesis is the dissociation of the reactants CH 4 and CO 2 . After the cold plasma has supplied the necessary energy for the dissociation of CH 4 and CO 2 , syngas, higher hydrocarbons, and oxygenates can be then easily produced. The present DFT study also demonstrates that the plasma synthesis will normally lead to a formation of a mixture of syngas, higher hydrocarbons, and oxygenates.

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“…Various non-precious-metal complexes have been investigated for homogeneous methanol carbonylation, but they show distinctly inferior performance in comparison to Ru or Ir without exception. − Modifications of [Rh(CO) 2 I 2 ] − by introducing electron-donating ligands have been attempted to improve the catalytic activity in methanol carbonylation, − while the output is somewhat limited. More importantly, the key issues of catalytic deactivation and separation in homogeneous systems remain unsolved. ,, In this context, the heterogenized carbonylation catalysts are coming into focus, and some alternative routes have been developed thereupon.…”

Section: Introductionmentioning

confidence: 99%

Stabilizing Isolated Rhodium Cations by MFI Zeolite for Heterogeneous Methanol Carbonylation

et al. 2021

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Methanol carbonylation is known as a classic reaction of homogeneous catalysis with large-scale industrial applications. The heterogenization of homogeneous catalysts is being pursued to address the issues of catalyst deactivation and separation encountered in homogeneous systems. Herein, we report the strategy of stabilizing isolated rhodium cations by MFI zeolite to construct highly active Rh@MFI zeolite catalysts for heterogeneous methanol carbonylation. The formation of a zeolite-stabilized [Rh(CO)2I2] analogue during the reaction has been identified to catalyze methanol carbonylation. Moreover, the structure of the zeolite can significantly promote methanol carbonylation within channels through electronic confinment. As a result, a state of the art turnover frequency of 3950 molacetyl/(molRh h) is achieved with the Rh@ZSM-5 catalyst at a low reaction temperature of 423 K. This work presents a simple and general approach toward the heterogenization of homogeneous catalysts for targeted chemical transformations.

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The mechanism of the phosphine-modified nickel-catalyzed acetic acid process

Cited by 27 publications

References 16 publications

Ligand Effects on Reactivity of Cobalt Acyl Complexes

Ligand Effects on Reactivity of Cobalt Acyl Complexes

Density Functional Theory Study of Synthesis of Oxygenates and Higher Hydrocarbons from Methane and Carbon Dioxide Using Cold Plasmas

Stabilizing Isolated Rhodium Cations by MFI Zeolite for Heterogeneous Methanol Carbonylation

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