Concentration oscillations in the oxidative carbonylation of non-1-yne in the PdI2-KI-CO-O2-CH3OH and PdI2-KI-CO-O2-phenylacetylene-CH3OH systems

Gorodsky, Sergey N.

doi:10.1134/s0023158412040027

Cited by 3 publications

(2 citation statements)

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“…12,13 Besides the sustained oscillations, the PCOC reaction has demonstrated a temperature-dependent product selectivity, which is potentially useful for industrial application due to a reduction of costs for isolation and purification, 14 applicable to a number of substrates, as demonstrated by Gorodsky. [15][16][17] Recently oscillations in pH were reported for PCOC, where an alkyne-functionalised polymeric substrate (poly(ethylene glycol)methyl ether acetylene, abbreviated as PEGA) was employed in place of PhAc, extending the opportunities of application of PCOC in smart materials. 13 Although the PCOC reaction in oscillatory mode has been studied in depth by Novakovic et al, Gorodsky and Temkin et al, the evidence for other palladium catalysts' activity displaying similar dynamics in this reaction system is lacking.…”

Section: Introductionmentioning

confidence: 99%

From small molecules to polymeric catalysts in the oscillatory carbonylation reaction: multiple effects of adding HI

Isakova

Murdoch

Novakovic

2018

Phys. Chem. Chem. Phys.

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The oscillatory palladium-catalysed carbonylation reaction opens new horizons for applications in smart materials due to the versatility of its conditions and substrates, as well as the adjustability of amplitude and period of pH oscillations. A variety of viable substrates have been demonstrated, including polymeric alkyne-terminated substrates. However, so far, there have not been any reports of polymer-based palladium catalysts in oscillatory mode. In this paper, we demonstrate pH oscillations in various systems, using commercially available palladium acetate, a triphenylphosphine palladium acetate complex and a polymer-bound palladium catalyst. While palladium acetate was able to generate oscillations under the conditions already established in our previous research on PdI2-catalysed oscillators, the other two catalysts needed the addition of HI to induce oscillations. HI forced an initial pH drop, bringing pH into the range where oscillations generally occur. Addition of HI had a significant effect on all catalysts, modifying the amplitude and period of oscillations, oscillation mode, as well as starting material conversion and product distribution.

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Section: Introductionmentioning

confidence: 99%

From small molecules to polymeric catalysts in the oscillatory carbonylation reaction: multiple effects of adding HI

Isakova

Murdoch

Novakovic

2018

Phys. Chem. Chem. Phys.

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show abstract

“…Oscillatory reactions are considered to be a powerful avenue for a smart self-pulsatile polymeric systems, if coupled to the right pH-, redox-or thermo-responsive polymer or hydrogel for a grand number of potential biomimetic applications [1][2][3]. Of the reported oscillatory reactions [4][5][6][7][8], palladium-catalysed oxidative carbonylation (PCOC) of alkynes (Scheme 1) is attracting attention as one of the most versatile reactions, capable of producing sustained (for up to one month of monitoring) oscillations in pH, redox potential, turbidity, and heater power (measured by power compensation calorimetry), where the amplitude and period can be successfully regulated by adjusting the reactant composition or temperature [9][10][11][12][13][14][15][16].…”

Section: Introductionmentioning

confidence: 99%