Improved Performance of a Europium‐based Metal‐Organic Framework for Cyanosilylation of Demanding Ketones

Pérez, Juana M.; Echenique‐Errandonea, Estitxu; Choquesillo‐Lazarte, Duane; Seco, José M.; López-Vargas, Mireya E.; Rodríguez‐Diéguez, Antonio; Fernández, Ignacio

doi:10.1002/cctc.202200967

Cited by 5 publications

(15 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Making use of the data obtained in the kinetic profiles, the turnover frequency (TOF) for all the GR-MOFs was calculated as a function of conversion (Figures S21-S24), obtaining a maximum TOF of 2640 h –1 at 1.5 min of reaction time (33% of conversion) with GR-MOF-14 and a second top value of 816 h –1 at 5 min of reaction time (34% of conversion) for GR-MOF-11 . These results remarkably overpass those found by our group with Y- and Eu-based MOF catalysts , but also those ever reported with any MOF based on lanthanide, Cd, or Ba metals (maximum TOF reported, 384 h –1 ) (Tables S8 and S9, note that Sr-based MOFs have never been reported in these catalytic reactions). ,− …”

Section: Resultsmentioning

confidence: 44%

Metal–Organic Frameworks Based on a Janus-Head Biquinoline Ligand as Catalysts in the Transformation of Carbonyl Compounds into Cyanohydrins and Alcohols

Pérez

Morales-Cámara

García-Salas

et al. 2022

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

A new family of metal–organic frameworks (MOFs) named GR-MOFs with the chemical formula {[M x (BCA) y ](H2O) z (DMF) w } (x,y,z,w: 1,1,2,0; 1,1.5,0,1; 1,2,2,1; and 1,1,0,2 for GR-MOF-11 to 14, respectively) based on s-block [M: Sr (GR-MOF-11), Ba (GR-MOF-14)] and d-block [M: Y (GR-MOF-12) and Cd (GR-MOF-13)] metals together with the biquinoline ligand 2,2′-bicinchoninic acid (H2BCA) has been synthetized by a solvothermal route and fully characterized by elemental and thermogravimetric analysis, Fourier transform infrared spectroscopy, photoluminescence, particle size distribution through optical microscopy, electrophoretic mobility, and finally, X-ray single-crystal and powder diffraction. The structural characterization reveals that these 2D and 3D MOFs possess a rich variety of coordination modes that maintained the Janus-head topology on the ligand in most of the cases. The new MOFs were studied in the catalyzed cyanosilylation and hydroboration of an extensive group of aldehydes and ketones, wherein the s-block metal-based MOFs GR-MOF-11 and GR-MOF-14 provided the highest efficiency ever reported in the MOF-catalyzed cyanosilylation of carbonyl compounds by using only 0.5 mol % of catalyst loading, room temperature, and solvent-free conditions. Furthermore, the hydroboration of ketones has been reported for the first time with this type of s-block metal catalysts obtaining from moderate to good conversions.

show abstract

Section: Resultsmentioning

confidence: 44%

Metal–Organic Frameworks Based on a Janus-Head Biquinoline Ligand as Catalysts in the Transformation of Carbonyl Compounds into Cyanohydrins and Alcohols

Pérez

Morales-Cámara

García-Salas

et al. 2022

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

show abstract

“…A switch from aromatic to aliphatic aldehydes (e.g., propionaldehyde, crotonaldehyde, and isovaleraldehyde) also resulted in excellent conversion (99.9%), expanding the choice of aldehydes. The recorded conversions for all of the substrates with MOF 1′ are higher than various other recently reported MOFs such as MOF-74@D2-MOF-74, Eu-MOF, D26-MOF-74, Tb-MOF, and GR-MOF . An elegant comparison to our work would be with that of Errandonea and co-workers, where 4-methoxybenzaldehyde required 48 h for complete conversion .…”

Section: Resultssupporting

confidence: 47%

Quest for a Desolvated Structure Unveils Breathing Phenomena in a MOF Leading to Greener Catalysis in a Solventless Setup: Insights from Combined Experimental and Computational Studies

Kumari,

Yadav,

Kumari

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

The crystal structure of the metal−organic framework (MOF), {Mn 2 (1,4-bdc) 2 (DMF) 2 } n (1) (1,4-bdcH 2 , 1,4-benzenedicarboxylic acid; DMF, N,N-dimethylformamide), is known for a long time; however, its desolvated structure, {Mn 2 (1,4-bdc) 2 } n (1′), is not yet known. The first-principles-based computational simulation was used to unveil the structure of 1′ that shows the expansion in the framework, leading to pore opening after the removal of coordinated DMF molecules. We have used 1′ that contains open metal sites (OMSs) in the structure in cyanosilylation and CO 2 cycloaddition reactions and recorded complete conversions in a solventless setup. The pore opening in 1′ allows the facile diffusion of small aldehyde molecules into the channels, leading to complete conversion. The reactions with larger aldehydes, 2-naphthaldehyde and 9anthracenecarboxaldehyde, also show 99.9% conversions, which are the highest reported until date in solventless conditions. The in silico simulations illustrate that larger aldehydes interact with Mn(II) OMSs on the surfaces, enabling a closer interaction and facilitating complete conversions. The catalyst shows high recyclability, exhibiting 99.9% conversions in the successive reaction cycles with negligible change in the structure. Our investigations illustrate that the catalyst 1′ is economical, efficient, and robust and allows reactions in a solventless greener setup, and therefore the catalysis with 1′ can be regarded as "green catalysis".

show abstract

“…carbonylic substrates. These novel systems represent an extension of our work on isostructural metal−organic frameworks based on Y, 34 Eu, 21 Y/Eu, 35 and Dy, 44 with the target of exploring how partial substitution by a second metal will enable the bimetallic system to exhibit synergistic catalytic effects.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The catalytic activity of our new heterobimetallic Y/Tb-MOF (0.5 mol %) and monometallic Tb-MOF (0.5 mol %) was first evaluated in the cyanosilylation of different ketones (1) using TMSCN as a nucleophile, solvent-free reaction conditions, and room temperature under a N 2 atmosphere. These conditions were used previously for the reported monometallic Y-or Eu-MOF, 19,21 bimetallic Y/ Eu-MOF, 35 and with catalyst GR-MOF-6. 19 First, the evaluation of the blank reaction using acetophenone (1a) was carried out, obtaining no product 2a after a reaction time of 24 h, whereas in the presence of the catalysts, quantitative conversions were achieved (entry 1, Table 1) after 24 h. To evaluate the scope of the reaction, ketones with different chemical natures such as aromatic with electrondonating groups (1b) and electron-withdrawing groups (1c), heteroaromatic (1d), and also bearing aliphatic substituents (1e) were tested (entries 2−5).…”

Section: ■ Introductionmentioning

confidence: 99%

“…The formation of C–C bonds by the addition of trimethylsilyl cyanide (TMSCN) to carbonyl compounds to form cyanohydrin trimethylsilyl ethers is another reaction of interest. The products of this reaction can be transformed into a wide range of new products or synthetic intermediates such as α-hydroxy acids, α-hydroxyaldehydes, and β-aminoalcohols. − This reaction has been studied using MOF catalysts based on Cu, Cr, Mn, Fe, Co, and Zr, among others, including RE-MOFs (Table S13). − Interestingly, most of these works focus on aldehydes as the most reactive substrates, with only few examples focused on the less reactive ketones .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Characterization, and Catalytic Performance of a New Heterobimetallic Y/Tb Metal–Organic Framework with High Catalytic Activity

López-Vargas,

Pérez,

Echenique-Errandonea

et al. 2024

ACS Omega

Self Cite

View full text Add to dashboard Cite

A three-dimensional heterobimetallic porous structure with the formula {[Y 3.5 Tb 1.5 L 6 (OH) 3 (H 2 O) 1.5 (DMF) has been synthesized and characterized by single crystal and powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), inductively coupled plasma mass spectrometry (ICP-MS), electrophoretic mobility, and Fourier transform infrared (FTIR) spectroscopy. The structure presents two metal environments: a bioaugmented isosceles wedge (mm2) MO 8 and a tricapped trigonal prism (−6m2) MN 3 O 6 . These configurations facilitate the creation of channels with a diameter of 10.7 Å, enabling its utilization as an active catalyst where the heterobimetallic nature of the assembly will be explored. This mixed-metal metal−organic framework has been tested in the cycloaddition of epoxides with carbon dioxide as well as in the cyanosilylation and hydroboration reactions of carbonylic substrates. Additionally, a monometallic Tb-MOF analogue has been synthesized for comparative evaluation of their catalytic performances. Both the mixed metal and monometallic variants exhibit outstanding activity in the cyanosilylation and hydroboration of carbonyls and in the synthesis of carbonates under CO 2 pressure. However, only the latter exhibits high recyclability.

show abstract

Improved Performance of a Europium‐based Metal‐Organic Framework for Cyanosilylation of Demanding Ketones

Cited by 5 publications

References 49 publications

Metal–Organic Frameworks Based on a Janus-Head Biquinoline Ligand as Catalysts in the Transformation of Carbonyl Compounds into Cyanohydrins and Alcohols

Metal–Organic Frameworks Based on a Janus-Head Biquinoline Ligand as Catalysts in the Transformation of Carbonyl Compounds into Cyanohydrins and Alcohols

Quest for a Desolvated Structure Unveils Breathing Phenomena in a MOF Leading to Greener Catalysis in a Solventless Setup: Insights from Combined Experimental and Computational Studies

Synthesis, Characterization, and Catalytic Performance of a New Heterobimetallic Y/Tb Metal–Organic Framework with High Catalytic Activity

Contact Info

Product

Resources

About