A micro-environment tuning approach for enhancing the catalytic capabilities of lanthanide containing polyoxometalate in the cyanosilylation of ketones

Nie, Yanmei; Li, Sang-Hao; Lin, Ming‐Yuan; Yan, Jun

doi:10.1039/d0cc01216e

Cited by 16 publications

(5 citation statements)

References 29 publications

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“…Several catalysts have been developed for the cyanosilylation of carbonyls, either under homogeneous − or heterogeneous conditions, − along with methodologies for recovering and reusing homogeneous catalysts. , From the sustainability point of view, easily separable solid catalysts are the preferable choice. The heterogeneous catalysts developed for cyanosilylation reactions may tentatively be classified into three major categories: (i) polyoxometalates, − which mainly act as Lewis bases; (ii) metal–organic frameworks − that exert mainly the role of Lewis acids; and (iii) organocatalysts (e.g., supported phosphine and supported ionic liquid-like phase , ). In comparison with the metal-based counterparts, organocatalysts are exempt from possible metal leaching and therefore from possible product contamination.…”

Section: Introductionmentioning

confidence: 99%

Waste-Minimized Cyanosilylation of Carbonyls Using Fluoride on Polymeric Ionic Tags in Batch and under Continuous Flow Conditions

Ferlin

Valentini

Brufani

et al. 2021

ACS Sustainable Chem. Eng.

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Herein, we report the development of a tailor-made fluoride-based heterogeneous catalyst, POLITAG-F, for the waste-minimized continuous production of cyanohydrin silyl ethers. The careful designing of the polymeric support and the choice of fluoride ion as the anionic species resulted in the improvement of catalytic efficiency and allowed the effective conversion of different carbonyls (aldehydes, ketones, and unsaturated ketones). The POLITAG-F catalyst, employed under flow conditions, led to the conversion of large amounts (over 100 mmol) of the substrate with a productivity of 0.1 mmol min–1. In addition, flow conditions allowed to minimize the waste production reaching an associated E-factor value of 0.04. An exhaustive evaluation of the environmental impact of our protocol has been reported by considering several green metrics (process mass intensity, atom economy, and reaction mass efficiency) and also the benign index and the safety hazard index of the process.

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Section: Introductionmentioning

confidence: 99%

Waste-Minimized Cyanosilylation of Carbonyls Using Fluoride on Polymeric Ionic Tags in Batch and under Continuous Flow Conditions

Ferlin

Valentini

Brufani

et al. 2021

ACS Sustainable Chem. Eng.

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“…Also, there are several examples that the outer surface of anionic POMs can be surrounded by organic cations (like TBA + ) 45,46 and in the case of our catalysts, 1 H NMR and 13 C NMR spectra provide clear and direct evidence for the presence of TBA + . For example, in the 1 H NMR, three peaks located separately around 1.35, 1.60, and 3.20 ppm can be assigned to the CH 2 of TBA + and the CH 3 group located at 0.96 ppm (Fig.…”

Section: Resultsmentioning

confidence: 66%

Incorporating heterogeneous lacunary Keggin anions as efficient catalysts for solvent-free cyanosilylation of aldehydes and ketones

Malmir

Heravi

Yekke-Ghasemi

et al. 2022

Sci Rep

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Polyoxometalates (POMs) as efficient catalysts can be used a wide range of chemical transformations due to their tunable Brønsted/Lewis-acidity and redox properties. Herein, we reported two hybrid and heterogeneous lacunary Keggin catalysts: (TBA)7[PW11O39] (TBA-PW11) and (TBA)8[SiW11O39]·4H2O (TBA-SiW11) (TBA+: tetrabutylammonium) in which [XW11O39]n− anions were coated by TBA+ cations. In this form, TBA+ can easily trap reactants on the surface of the catalysts and increase the catalytic reaction. Therefore, the catalytic performance of both POMs was tested in cyanosilylation of numerous compounds bearing-carbonyl group and trimethylsilyl cyanide under solvent-free conditions. TBA-PW11 is more effective than TBA-SiW11, conceivably due to the higher Lewis acidity of the P than the Si center and to the higher accessibility of the metal centers in the framework structure. Noteworthy, the recyclability and heterogeneity of both POMs catalysts were also examined, and the results confirmed that they remain active at least after three recycling procedures.

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“…Up to now, hourglass-type phosphomolybdate clusters {M[P 4 Mo V 6 O 31 ] 2 } n− (abbreviated as M{P 4 Mo 6 } 2 , where M represents metal ions), have drawn considerable interest in photocatalysis and electrochemical detection fields owing to their excellent redox capability and semiconductor-like optical property [31][32][33][34][35][36][37][38][39]. Especially, all the Mo atoms in the M{P 4 Mo 6 } 2 cluster are in the +5 oxidation state [40], which endows them with high reducibility and a wide spectral absorption range that can be extended to the visible and even infrared light regions [34][35][36][37]. Moreover, the M{P 4 Mo 6 } 2 cluster has high electrochemical stability and can withstand continuous reversible electron gain and loss processes while maintaining structural integrity.…”

Section: Introductionmentioning

confidence: 99%

Reduced phosphomolybdate as photoassisted electrochemical crystalline sensor for trace Cr(VI) detection

Song,

Guo,

Wang

et al. 2024

Polyoxometalates

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The development of a sensitive and efficient detection technology for trace toxic hexavalent chromium (Cr(VI)) in water is a pressing concern. In this study, an hourglass-type phosphomolybdate-based metal-organic network with the formula [Na 0.5 Cu 5.5 (H 2 O) 2 (btmbp) 4 ] [Mn(H 2 O) 3 ] 2 {Mn[H 6 P 4 Mo 6 O 31 ] 2 }•10H 2 O (1, btmbp = 4,4'-bis((1H-1,2,4-triazol-1-yl)methyl)biphenyl) was hydrothermally synthesized. The crystal network consists of a ladder-like two-dimensional layered structure constructed by vertical connections of onedimensional (1D) [Na 0.5 Cu 5.5 (H 2 O) 2 (btmbp) 4 ] 6+ metal-organic chains and 1D inorganic polyanionic chains. Compound 1 exhibits excellent electrochemical property and a wide light absorption range including visible light to accelerate the electron transfer in redox processes. When serving as a photoassisted electrochemical (PAEC) sensor for trace Cr(VI) detection, compound 1 exhibits a high sensitivity of 330.5 μA•μM −1 and a low detection limit of 0.95 nM (98.79 ppt) along with high anti-interference ability and excellent PAEC detection stability, outperforming most reported polyoxometalate-based sensors and equaling noble-metal sensors, far satisfying World Health Organization standards for Cr(VI) concentration in drinking water. This work provides a new photoelectrochemical sensor material for monitoring environmental pollutants.

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A micro-environment tuning approach for enhancing the catalytic capabilities of lanthanide containing polyoxometalate in the cyanosilylation of ketones

Abstract: A polyoxometalate molecule based catalyst manifested the highest catalytic activities, and the catalytic activities improved greatly through micro-environment tuning.

Cited by 16 publications

References 29 publications

Waste-Minimized Cyanosilylation of Carbonyls Using Fluoride on Polymeric Ionic Tags in Batch and under Continuous Flow Conditions

Waste-Minimized Cyanosilylation of Carbonyls Using Fluoride on Polymeric Ionic Tags in Batch and under Continuous Flow Conditions

Incorporating heterogeneous lacunary Keggin anions as efficient catalysts for solvent-free cyanosilylation of aldehydes and ketones

Reduced phosphomolybdate as photoassisted electrochemical crystalline sensor for trace Cr(VI) detection

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