A Mixed Heterobimetallic Y/Eu-MOF for the Cyanosilylation and Hydroboration of Carbonyls

Abstract

Supplementary Materials The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal12030299/s1. Table S1: Elemental analysis of compounds Y/Eu-MOF. Table S2: ICP-AES results of compound Y/Eu-MOF. Table S3: Crystallographic data and structure refinement details of compound Y/Eu-MOF. Table S4: Selected bond lengths (Å) and angles (°) for compound Y/Eu-MOF. Table S5: Table of the continuous Shape Measurements for the MN3O6 coordination environment. Table S6: Table of the continuous Shape Measurements for the MO8 coordination environment. Table S7: Electrophoretic mobility and ζ-potential dependence, with the pH of the Y/Eu-MOFs particles dispersed in water. Conductivity fixed at 330 µS/cm. Table S8: Optimization of the reaction conditions in the hydroboration reaction. Table S9: Green metrics calculated for Y/Eu-MOF catalyst. Table S10: Catalytic cyanosilylation of benzaldehyde performances of Ln-MOFs, as reported in the literature. Figure S1: Figure of the pattern matching analysis and experimental PXRD for Y/Eu-MOF. Figure S2: Figure of the infrared spectra of the ligand and Y/Eu-MOF. Figure S3: SEM and EDS mapping of bulk material of Y/Eu-MOF. Figure S4: Images and particle size distribution (an overall of 250 particles) in the deposited fraction of Y/Eu-MOF catalyst non-suspended in water (about a 68% of the total amount), determined from optical microscope images. Figure S5: Images and particle size distribution (an overall of 250 particles) of Y/Eu-MOF crystals in the fraction steadily suspended in water (about a 32% of the total amount), determined from optical microscope images. Figure S6: Comparation of the particle size distribution of Y/Eu-MOF in the fraction steadily suspended in water and the non-suspended, determined from optical microscope images. Figure S7: Calibration line of conductivity (µS/cm) vs [NaCl] (mol/L). Figure S8: ζ-potential (mV) dependence with the pH of the Y/Eu-MOF. All the measurements were performed with constant conductivity of 330 µS/cm. Figure S9: Electrophoretic mobility (µm·cm/V·s) dependence with the pH of the Y/Eu-MOF. All the measurements were performed with constant conductivity of 330 µS/cm. Figure S10: Study of the recyclability of Y/Eu-MOF (0.5 mol%) catalyst on the cyanosilylation and hydroboration reaction of acetophenone as carbonyl substrate. Figure S11: Analysis of the TOF (h−1) obtained in the cyanosilylation reaction of acetophenone at different times of reaction with Y/Eu-MOF (0.5 mol%), with the optimized reaction conditions. Figure S12: Analysis of the TOF (h−1) obtained in the hydroboration reaction acetophenone at different times of reaction with Y/Eu-MOF (0.5 mol%), with the optimized reaction conditions. Scheme S1: Reaction conditions used for the study of recyclability of Y/Eu-MOF catalysts in the cyanosilylation reaction. Scheme S2: Reaction conditions used for the study of recyclability of Y/Eu-MOF catalysts in the hydroboration reaction. Scheme S3: Leaching test, carried out after the first and second cycles.Funding: This research has been funded by the State Research Agency (grants CTQ2017-84334-R and PGC2018-102052-B-C21) of the Spanish Ministry of Science, Innovation and Universities, the European Union (European Regional Development Fund—ERDF), Junta de Andalucía (P20_01041, UAL2020-AGR-B1781, B-FQM-734-UGR20 and FQM-394). E.E., S.R., and J.P. acknowledge the Government of the Basque Country, Juan de la Cierva Incorporación (grant no. IJC2019-038894-I) and University of Almeria (grant no. HIPATIA2021_04) for their respective fellowsHerein, to the best of our knowledge, the first heterobimetallic Y/Eu porous metal–organic framework (MOF), based on 3-amino-4-hydroxybenzoic acid (H2L) ligand, with the following formulae {[Y3.5Eu1.5L6(OH)3(H2O)3]·12DMF}n (in advance, namely Y/Eu-MOF), is described. The three-dimensional structure has been synthesized by solvothermal routes and thoroughly characterized, by means of single crystal X-ray diffraction, powder X-ray diffraction, electronic microscopy, ICP-AES, electrophoretic mobility, and FTIR spectra. Intriguingly, the porous nature allows for coordinated solvent molecules displacement, yielding unsaturated metal centers, which can act as a Lewis acid catalyst. This novel supramolecular entity has been tested in cyanosilylation and hydroboration reactions on carbonyl substrates of a diverse nature, exhibiting an extraordinary activity.Cierva Incorporación IJC2019-038894-IState Research Agency CTQ2017-84334-R, PGC2018-102052-B-C21University of Almeria HIPATIA2021_04Ministerio de Ciencia, Innovación y UniversidadesEuropean CommissionEuropean Regional Development FundJunta de Andalucía B-FQM-734-UGR20, FQM-394, IJC2019-038894-I, P20_01041, UAL2020-AGR-B178