The use of an ultrahigh magnetic field spectrometer and 95Mo isotope enrichment facilitate the direct observation of the local structure of Mo species on Mo/zeolite catalysts by 95Mo NMR. Top trace: The experimental 95Mo NMR spectrum of 6Mo/HZSM-5. Bottom traces: The simulated overall spectrum (orange), the spectral component corresponding to MoO3 (purple), and the component corresponding to the exchanged Mo species (green). The exchanged Mo species proved to be the active center for the methane dehydroaromatization (MDA) reaction.
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http://dx.doi.org/10.1021/ja7110916 | DOI Listing |
Inorg Chem
May 2024
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany.
In contrast to a tungsten nitrido complex endowed with a tripodal silanolate ligand framework, which was reported in the literature to be a dimeric species with a metallacyclic core, the corresponding molybdenum nitrides are monomeric entities comprising a regular terminal nitride unit, as proven by single-crystal X-ray diffraction (SC-XRD). Their electronic character is largely determined by the constraints imposed on the metal center by the podand ligand architecture. Mo nuclear magnetic resonance (NMR) and, to a lesser extent, N NMR spectroscopy allow these effects to be studied, which become particularly apparent upon comparison with the spectral data of related molybdenum nitrides comprising unrestrained silanolate, alkoxide, or amide ligands.
View Article and Find Full Text PDFJ Am Chem Soc
December 2023
Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim/Ruhr, Germany.
Molybdenum alkylidynes endowed with tripodal silanolate ligands belong to the most active and selective catalysts for alkyne metathesis known to date. This paper describes a new generation that is distinguished by an unprecedented level of stability and practicality without sacrificing the chemical virtues of their predecessors. Specifically, pyridine adducts of type are easy to make on gram scale, can be routinely weighed and handled in air, and stay intact for many months outside the glovebox.
View Article and Find Full Text PDFDalton Trans
August 2023
Departamento de Biología y Geología, Física y Química Inorgánica, Escuela Superior de Ciencias Experimentales y Tecnología, Universidad Rey Juan Carlos, 28933 Móstoles, Madrid, Spain.
Polyoxometalate (POM) mesoporous silica-based materials with a low POM loading have been designed with hydrophilic and hydrophobic properties. These materials act as powerful heterogeneous catalysts in oxidative desulfurization (ODS), owing to their ability to adsorb both HO and sulphur-containing compounds from the model oil simultaneously. The formation of charge transfer salts through ion pair interaction with a choline functionality, available on the hybrid silica support, affords robust and recyclable heterogeneous catalysts for the ODS process under mild conditions (45 min and 40 °C).
View Article and Find Full Text PDFJ Am Chem Soc
June 2023
Department of Chemistry and Applied Biosciences, ETH Zürich, Zürich CH-8093, Switzerland.
The olefin metathesis activity of silica-supported molybdenum oxides depends strongly on metal loading and preparation conditions, indicating that the nature and/or amounts of the active sites vary across compositionally similar catalysts. This is illustrated by comparing Mo-based (pre)catalysts prepared by impregnation (2.5-15.
View Article and Find Full Text PDFInorg Chem
February 2023
Institut Lavoisier de Versailles, CNRS, UVSQ, Université Paris-Saclay, 45 avenue des Etats-Unis, 78035Versailles, France.
Polyoxometalates (POMs) represent a promising class of molecular electron reservoirs. However, their multielectron reduction gives rise to intricate physical-chemical phenomena that must be fully understood for their future use in energy-storage devices. Herein, we show that bulk electrolysis of the archetypal Keggin-type POM [Si(WMoO)(WO)] in aqueous solution leads to the six-electron-reduced derivative [Si(WMoO(HO))(WO)] (notated ) in which the mixed-metal triad acts as a storage unit for six electrons and six protons.
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