Engineering catalytic coordination space in a chemically stable Ir-porphyrin MOF with a confinement effect inverting conventional Si–H insertion chemoselectivity† †Electronic supplementary information (ESI) available: Physical characterization of metalloporphyrin ligands, crystal structure data, physical characterization, chemical/thermal stability studies, gas adsorption of porphyrinic MOFs, recycling experiments, and NMR data of Si–H insertion products. CCDC 1491233. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc03288e Click here for additional data file. Click here for additional data file.
نویسندگان
چکیده
An iridium-porphyrin ligand, Ir(TCPP)Cl (TCPP 1⁄4 tetrakis(4-carboxyphenyl)porphyrin), has been utilized to react with HfCl4 to generate a stable Ir(III)-porphyrin metal–organic framework of the formula [(Hf6(m3O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3]$solvents (Ir-PMOF-1(Hf)), which possesses two types of open cavities (1.9 1.9 1.9 and 3.0 3.0 3.0 nm) crosslinked through orthogonal channels (1.9 1.9 nm) in three directions. The smaller cavity is surrounded by four catalytic Ir(TCPP)Cl walls to form a confined coordination space as a molecular nanoreactor, while the larger one facilitates reactant/product feeding and release. Therefore, the porous Ir-PMOF-1(Hf) can act as a multi-channel crystalline molecular flask to promote the carbenoid insertion reaction into Si–H bonds, featuring high chemoselectivity towards primary silanes among primary, secondary and tertiary silanes under heterogeneous conditions that are inaccessible by conventional homogeneous catalysts.
منابع مشابه
AuICl-bound N-heterocyclic carbene ligands form MII4(LAuCl)6 integrally gilded cages† †Electronic supplementary information (ESI) available: Experimental procedures, synthesis and characterization data for subcomponents and cages, and optical, microscopy, ESI-MS and NMR data. CCDC 1061936. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03065j Click here for additional data file. Click here for additional data file.
متن کامل
Gold(iii)–arene complexes by insertion of olefins into gold–aryl bonds† †Electronic supplementary information (ESI) available: Experimental details (syntheses, analytical data and copies of 1H, 13C and 31P NMR spectra), crystallographic data of 2 and computational details. CCDC 1526613 and 1538015. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00145b Click here for additional data file. Click here for additional data file.
متن کامل
Photoinduced single-crystal-to-single-crystal phase transition and photosalient effect of a gold(i) isocyanide complex with shortening of intermolecular aurophilic bonds† †Electronic supplementary information (ESI) available: X-ray crystallographic data, optical properties, DFT calculations, and other additional information. CCDC [987280 and 987281]. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02676d Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file.
متن کامل
All-metal aromatic cationic palladium triangles can mimic aromatic donor ligands with Lewis acidic cations† †Electronic supplementary information (ESI) available: Reaction procedures, characterization of complexes, copies of all spectra and cif files, modelling details and XYZ coordinates. CCDC 1410440–1410442. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03475j Click here for additional data file. Click here for additional data file.
متن کامل
Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts† †Electronic supplementary information (ESI) available: Experimental details, material characterization data, catalytic measurement details and crystallographic details. CCDC 1499756. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05178b Click here for additional data file. Click here for additional data file.
متن کامل