Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes

Khabibulin, Vildar R.; Kulik, Аlexander; Oshanina, I. V.; Брук, Л. Г.; Темкин, О. Н.; Nosova, V. M.; Ustynyuk, Yu. A.; Bel’skii, V. K.; Сташ, А. И.; Лысенко, К. А.; Antipin, M. Yu.

doi:10.1134/s0023158407020073

Cited by 16 publications

(8 citation statements)

References 20 publications

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“…The proton resonances of the aromatic protons of the triphenyl phosphine moieties are significantly shifted to lower field, indicating complexation. The 31 P{ 1 H} NMR resonance of the macroligand (−4.99 ppm) completely shifts downfield (23.53 ppm) after the complex formation, evidencing quantitative complexation based on the 31 P{ 1 H} NMR data of [Pd(PPh 3 ) 2 Cl 2 ], where the phosphor resonance appears at 23.88 ppm . The 31 P{ 1 H} NMR spectra of the macroligands and SCMCs exhibit a resonance close to 28 ppm, which is assigned to the oxidized phosphine moiety (PO) .…”

Section: Resultsmentioning

confidence: 89%

Single‐Chain Self‐Folding of Synthetic Polymers Induced by Metal–Ligand Complexation

Willenbacher

Altintas

Roesky

et al. 2013

Macromol. Rapid Commun.

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The controlled folding of a single polymer chain is for the first time realized by metal- complexation. α,ω-Bromine functional linear polymers are prepared via activators regenerated by electron transfer (ARGET) ATRP (M¯n,SEC = 5900 g mol(-1) , Đ = 1.07 and 12 000 g mol(-1) , Đ = 1.06) and the end groups of the polymers are subsequently converted to azide functionalities. A copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is carried out in the presence of a novel triphenylphosphine ligand and the polymers to afford homotelechelic bis-triphenylphosphine polymeric-macroligands (MLs) (M¯n,SEC = 6600 g mol(-1) , Đ = 1.07, and 12 800 g mol(-1) , Đ = 1.06). Single-chain metal complexes (SCMCs) are formed in the presence of Pd(II) ions in highly diluted solution at ambient temperature. The results derived via (1) H and (31) P{(1) H} NMR experiments, SEC, and DLS unambiguously evidence the efficient formation of SCMCs via metal ligand complexation.

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Section: Resultsmentioning

confidence: 89%

Single‐Chain Self‐Folding of Synthetic Polymers Induced by Metal–Ligand Complexation

Willenbacher

Altintas

Roesky

et al. 2013

Macromol. Rapid Commun.

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“…Mixed-mode oscillations after addition of HI For phosphine-bound Pd catalysts (L-Cat and P-Cat), pH did not reach the values where oscillations typically occurred in previous oscillatory carbonylation reactions. 7,10,13,17 Therefore, three catalysts were examined further in a new set of experiments where pH was artificially decreased by the addition of HI after the addition of substrate (Fig. 3).…”

Section: Single Mode Oscillations In Pdacmentioning

confidence: 99%

“…[3][4][5] The palladium-catalysed oxidative carbonylation (PCOC) reaction has recently attracted attention due to its ability to exhibit oscillations in pH, redox potential, turbidity and heat of reaction. [6][7][8] The most studied system employs phenylacetylene (PhAc) as substrate due to the facile analysis of products 9 and uses PdI 2 as a catalyst. Oscillations in the PhAc/PdI 2 system are sustained in a batch reactor for days of monitoring with the possibility of varying the amplitude and period of oscillations by adjusting the temperature of reaction, 10,11 concentration of the catalyst, substrate or even water content.…”

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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“…As the reductant (substrate) is consumed, the main role is played by the 7) with the participation of Н + and the regeneration of active Pd 2+ and species. Published data suggest that the system under consideration may also contain other complex species, including [179], Pd 2 SO 4 (Q) [180], LPdQ (L = 1.5 cyclooctadiene) [181], and PddQ complexes with Q and triphenylphosphin [182]. Detailed mechanistic schemes of cyclohexene conversions in this system are presented in [145].…”

Section: Arylation Of Olefins Via the Heck (Heck-mizoroki) Reaction Imentioning

confidence: 97%

Kinetic models of multi-route reactions in homogeneous catalysis with metal complexes (A Review)

Темкин

2012

Kinet Catal

Self Cite

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The state of the art in the theory of routes for multi route reactions in the homogeneous catalysis with metal complexes is reviewed. Key problems and the possible approaches to their solution based on the Horiuti-Temkin theory of steady state reactions, which are useful in constructing the kinetic algebraic mod els of multi route processes, are discussed. A classification of the mechanisms of real processes involved in the homogeneous catalysis with metal complexes is presented. The chain mechanisms of catalytic processes, conjugated and associated reactions, and critical phenomena in the dynamics of homogeneous reactions are considered.

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Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes

Cited by 16 publications

References 20 publications

Single‐Chain Self‐Folding of Synthetic Polymers Induced by Metal–Ligand Complexation

Single‐Chain Self‐Folding of Synthetic Polymers Induced by Metal–Ligand Complexation

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

Kinetic models of multi-route reactions in homogeneous catalysis with metal complexes (A Review)

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