An Amorphous Teflate Doped Aluminium Chlorofluoride: A Solid Lewis‐Superacid for the Dehydrofluorination of Fluoroalkanes

An anion-doped aluminium chlorofluoride AlCl0.1F2.8(OTeF5)0.1 (ACF-teflate) was synthesized. The material contains pentafluoroorthotellurate (teflate) groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR-IR spectra of adsorbed CD3CN reveal a blue-shift of the adsorption band by 73 cm−1, which is larger than the shift for SbF5. Remarkably, ACF-teflate catalyzes dehydrofluorination reactions of monofluoroalkanes to yield olefins in C6D6. In these cases, no Friedel-Crafts products were formed.German Research Foundation http://dx.doi.org/10.13039/501100001659Diamond Light Source http://dx.doi.org/10.13039/100011889German Research Foundation http://dx.doi.org/10.13039/501100001659Peer Reviewe

An Amorphous Teflate Doped Aluminium Chlorofluoride: A Solid Lewis‐Superacid for the Dehydrofluorination of Fluoroalkanes

An anion‐doped aluminium chlorofluoride AlCl0.1F2.8(OTeF5)0.1 (ACF‐teflate) was synthesized. The material contains pentafluoroorthotellurate (teflate) groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR‐IR spectra of adsorbed CD3CN reveal a blue‐shift of the adsorption band by 73 cm−1, which is larger than the shift for SbF5. Remarkably, ACF‐teflate catalyzes dehydrofluorination reactions of monofluoroalkanes to yield olefins in C6D6. In these cases, no Friedel‐Crafts products were formed

A Combined Mg-25 Solid-State NMR and Ab Initio DFT Approach to Probe the Local Structural Differences in Magnesium Acetate Phases Mg(CH3COO)(2)center dot nH(2)O (n=0,1,4)

Multinuclear (H-1, C-13, Mg-25) solid-state NMR data is reported for a series of magnesium acetate phases Mg(CH3COO)(2)nH(2)O (n=0 (two polymorphs), 1, 4). The central focus here is Mg-25 as this set of compounds provides an expanded range of local magnesium coordinations compared to what has previously been reported in the literature using NMR. These four compounds provide 10 distinct magnesium sites with varying NMR interaction parameters. One of the anhydrous crystal structures () has an MgO7 site which is reported, to the best of our knowledge, for the first time. For those phases with a single crystal structure, a combination of magic angle spinning (MAS) NMR at high magnetic field (20T) and first principles density functional theory (DFT) calculations demonstrates the value of including Mg-25 in NMR crystallography approaches. For the second anhydrate phase (), where no single crystal structure exists, the multinuclear NMR data clearly show the multiplicity of sites for the different elements, with Mg-25 satellite transition (ST) MAS NMR revealing four inequivalent magnesium environments, which is new information constraining future refinement of the structure. This study highlights the sensitivity of Mg-25 NMR to the local environment, an observation important for several sub-disciplines of chemistry where the structural chemistry of magnesium is likely to be crucial

Vanadiumdotierte Metalloxide und -oxofluoride als Katalysatoren in selektiven Oxidationsreaktionen

In der vorliegenden Arbeit wurden unter Anwendung unterschiedlicher Präparationstechniken vanadiumdotierte Metalloxide bzw. –oxofluoride synthetisiert, umfassend charakterisiert und in katalytischen, selektiven Oxidationsreaktionen (ODH von Propan und Methanoloxidation) getestet. Die Festkörper- und oberflächenchemischen Eigenschaften wurden generell mittels CHN-Analyse, ICP-OES, XRD, Raman-, FTIR-, MAS-NMR- und ESR-Spektroskopie, Py-PAS, TPD und Tieftemperatur-Stickstoffadsorption untersucht. Ergänzend kamen an ausgewählten Proben der temperaturprogrammierte Sauerstoffisotopenaustausch und Adsorptionsuntersuchungen von Methanol zum Einsatz. Als katalytische Testreaktionen dienten die oxidative Dehydrierung von Propan und die selektive Methanoloxidation. Unabhängig von der angewendeten Synthesemethode zeigte sich, dass die Festkörpereigenschaften sowohl durch den Vanadiumgehalt, als auch wesentlich durch die Art des Wirtsgitters beeinflusst werden. Es konnte nachgewiesen werden, dass eine hohe Sauerstoffaustauschaktivität und das Vorhandensein Brønsted-saurer Zentren auf den Katalysatoroberflächen die Aktivierung der Edukte in den hier untersuchten katalytischen Reaktionen begünstigen. In Bezug auf die Selektivität zu den Zielprodukten Propen bzw. Formaldehyd sind diese Eigenschaften allerdings nachteilig, da an derartigen Zentren immer die Produkte der Totaloxidation (CO und CO2) gebildet werden. Besonders bemerkenswert ist das Verhalten der vanadiumdotierten Aluminiumoxofluoride. Diese Phasen wurden mit einer neuen Methode synthetisiert und enthalten fast ausschließlich Lewis-saure Zentren. Die Matrix wird zudem maßgeblich durch die Fluoridionen bestimmt, sodass die Sauerstoffmobilität und –austauschaktivität sehr gering sind. Dadurch reagieren sie, trotz einer relativ hohen katalytischen Aktivität, außerordentlich selektiv in den hier untersuchten selektiven Oxidationsreaktionen.In this thesis, vanadium containing metal oxides and oxyfluorides were prepared, thoroughly characterised and tested as catalysts in selective oxidation reactions. Bulk and surface properties of all samples were studied by means of CHN-analysis, ICP-OES, XRD, Raman-, FTIR-, MAS-NMR- und ESR-spectroscopy, Py-PAS, TPD and BET-adsorption. Moreover, the oxygen isotope exchange behaviour and the methanol adsorption properties of selected samples were analysed in order to correlate the surface properties with the catalytic behaviour of the materials. Irrespective of the preparation technique applied, the properties of the solids strongly depend on the host lattice as well as on the vanadium content. It has been clearly revealed that a high oxygen exchange activity and the presence of Brønsted acid sites on the catalyst surface promote the activation of the educts in selective oxidation reactions. The enhanced activity, however, is generally accompanied by a low selectivity towards the desired products propylene and formaldehyde, respectively. The low selectivity is caused by the high concentration of catalytically active sites leading to the formation of carbon oxides as total oxidation products of propane and methanol. A very promising catalytic behaviour was observed with vanadium-doped aluminium oxyfluorides. The oxyfluorides were prepared by a new method and contain almost exclusively Lewis-acid sites. The matrix is mainly determined by the fluoride anions resulting in a reduced oxygen mobility and exchange activity. Hence, the vanadium-doped aluminium oxyfluorides exhibit a relatively high catalytic activity accompanied by an excellent selectivity in the oxidation reaction of propane and methanol

Fluorolytic Sol–Gel Synthesis of Nanometal Fluorides: Accessing New Materials for Optical Applications

The potential of fluorolytic sol⁻gel synthesis for a wide variety of applications in the field of optical materials is reviewed. Based on the fluorolytic sol⁻gel synthesis of nanometal fluorides, sols of complex fluorometalates have become available that exhibit superior optical properties over known classical binary metal fluorides as, for instance, magnesium fluoride, calcium fluoride, or strontium fluoride, respectively. The synthesis of transparent sols of magnesium fluoroaluminates of the general composition MgxAlFy, and fluoroperovskites, [K1−xNax]MgF3, is reported. Antireflective coatings fabricated from MgF2, CaF2, MgxAlFy, and [K1−xNax]MgF3 sols and their relevant properties are comprehensively described. Especially the heavier alkaline earth metal fluorides and the fluorperovskites crystallizing in a cubic crystal structure are excellent hosts for rare earth (RE) metals. Thus, the second chapter reflects the synthesis approach and the properties of luminescent systems based on RE-doped alkaline earth metal fluorides and [K1−xNax]MgF3 phases

Sol-Gel-Synthesis of Nanoscopic Complex Metal Fluorides

The fluorolytic sol-gel synthesis for binary metal fluorides (AlF3, CaF2, MgF2) has been extended to ternary and quaternary alkaline earth metal fluorides (CaAlF5, Ca2AlF7, LiMgAlF6). The formation and crystallization of nanoscopic ternary CaAlF5 and Ca2AlF7 sols in ethanol were studied by 19F liquid and solid state NMR (nuclear magnetic resonance) spectroscopy, as well as transmission electron microscopy (TEM). The crystalline phases of the annealed CaAlF5, Ca2AlF7, and LiMgAlF6 xerogels between 500 and 700 °C could be determined by X-ray powder diffraction (XRD) and 19F solid state NMR spectroscopy. The thermal behavior of un-annealed nanoscopic ternary and quaternary metal fluoride xerogels was ascertained by thermal analysis (TG/DTA). The obtained crystalline phases of CaAlF5 and Ca2AlF7 derived from non-aqueous sol-gel process were compared to crystalline phases from the literature. The corresponding nanoscopic complex metal fluoride could provide a new approach in ceramic and luminescence applications.Peer Reviewe

Exploring the Role of Solvent Polarity in Mechanochemical Knoevenagel Condensation: In-situ Tracking and Isolation of Reaction Intermediates

Mechanochemistry has proven to be a highly effective method for the synthesis of organic compounds. We studied the kinetics of the catalyst-free Knoevenagel reaction between 4-nitrobenzaldehyde and malononitrile, activated and driven by ball milling. The reaction was investigated in the absence of solvents (neat grinding) and in the presence of solvents with different polarities (liquid-assisted grinding). The reaction was monitored using time-resolved in-situ Raman spectroscopy and powder X-ray diffraction (PXRD). Our results indicate a direct relationship between solvent polarity and reaction kinetics, with higher solvent polarity leading to faster product (2-(4-nitrobenzylidone)malononitrile) formation. For the first time, we were able to isolate and determine the structure of an intermediate 2-(hydroxy(4-nitrophenyl)methyl)malononitrile based on PXRD dat

An Amorphous Teflate Doped Aluminium Chlorofluoride: A Solid Lewis Superacid for the Dehydrofluorination of Fluoroalkanes

An anion doped aluminium chlorofluoride AlCl0.1F2.8(OTeF5)0.1 (ACF-teflate) was synthesized. The material contains pentafluoroorthotellurate (teflate) groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR-IR spectra of adsorbed CD3CN reveal a blue-shift of the adsorption band by 73 cm1, which is larger than the shift for SbF5. Remarkably, ACF-teflate catalyzes dehydrofluorination reactions of monofluoroalkanes to yield olefins in C6D6. In these cases, no Friedel-Crafts products were formed