Mechanochemical Synthesis and Magnetic Properties of the Mixed-Valent Binary Silver(I,II) Fluorides, AgAgF and AgAgF.

Fluoridoargentates(II) represent a fascinating class of silver(II) compounds with structural and magnetic similarities to cuprate superconductors. However, their synthesis is challenging, leaving their properties largely underexplored and hindering the discovery of new phases. This study introduces mechanochemistry as a novel approach for the synthesis of fluoridoargentates(II), avoiding the use of anhydrous HF or elemental fluorine and employing readily available equipment.

Reactive Noble-Gas Compounds Explored by 3D Electron Diffraction: XeF-MnF Adducts and a Facile Sample Handling Procedure.

Recent advances in 3D electron diffraction (3D ED) have succeeded in matching the capabilities of single-crystal X-ray diffraction (SCXRD), while requiring only submicron crystals for successful structural investigations. One of the many diverse areas to benefit from the 3D ED structural analysis is main-group chemistry, where compounds are often poorly crystalline or single-crystal growth is challenging. A facile method for loading and transferring highly air-sensitive and strongly oxidizing samples at low temperatures to a transmission electron microscope (TEM) for 3D ED analysis was successfully developed and tested on xenon(II) compounds from the XeF-MnF system.

Charge Density Study of Two-Electron Four-Center Bonding in a Dimer of Tetracyanoethylene Radical Anions as a Benchmark for Two-Electron Multicenter Bonding.

The dimer of the tetracyanoethylene (TCNE) radical anions represents the simplest and the best studied case of two-electron multicenter covalent bonding (2e/mc or ). The model compound, -methylpyridinium salt of TCNE, is diamagnetic, meaning that the electrons in two contiguous radicals are paired and occupy a HOMO orbital which spans two TCNE radicals. Charge density in this system is studied as a benchmark for comparison of charge densities in other pancake-bonded radical systems.

Probing Alzheimer's pathology: Exploring the next generation of FDDNP analogues for amyloid β detection.

Fluorescent probes are a powerful tool for imaging amyloid β (Aβ) plaques, the hallmark of Alzheimer's disease (AD). Herein, we report the synthesis and comprehensive characterization of 21 novel probes as well as their optical properties and binding affinities to Aβ fibrils. One of these dyes, 1Ae, exhibited several improvements over FDDNP, an established biomarker for Aβ- and Tau-aggregates.

Towards structurally versatile mesoionic N-heterocyclic olefin ligands and their coordination to palladium, gold, and boron hydride.

We have developed an efficient and versatile approach for the synthesis of a family of 1,2,3-triazole-based mesoionic N-heterocyclic olefin (mNHO) ligands and investigated their coordination to palladium, gold, and boron hydride experimentally and computationally. We reacted mNHOs obtained through deprotonation of the corresponding methylated and ethylated 1,3,4-triaryl-1,2,3-triazolium salts with [Pd(allyl)Cl] to give the corresponding [Pd(η-allyl)Cl(mNHO)] coordination complexes. C NMR data revealed the strong σ-donor character of the mNHO ligands, consistent with the calculated bond orders and atom-condensed charges.

Crystal structure of CaSiF·2HO(2) and reevaluation of the Si-F bond-valence parameter .

The structure of a second polymorph of CaSiF·2HO [calcium hexafluorido-silicate dihydrate; space group 2/ (No. 13), Pearson symbol 2] was elucidated by single-crystal X-ray diffraction. It arose as an unexpected product when soda-lime glass was attacked by HF.

Bis-(di-meth-oxy-ethane-1κ,')penta-kis-(1,1,1,3,3,3-hexa-fluoro-propan-2-olato)-2κ,3κ-μ-hy-droxido-1:3κ-μ-oxido-1:2:3κ-magnesiumdialuminium.

Partial hydrolysis of a sample of [Mg(dme)][Al(hfip)] crystals led to the formation of the title complex, [Mg(dme){HOAl(hfip)OAl(hfip)}] (dme = di-meth-oxy-ethane and hfipH = hexa-fluoro-iso-propanol) or [Mg(CHO)O(OH)Al(CHFO)]. The magnesium cation exhibits a distorted octa-hedral coordination with two bidentate di-meth-oxy-ethane mol-ecules and a dinuclear aluminate anion, coordinated to Mg oxido and hydroxido units. The anion is an oxido-bridged species, [HOAl(hfip)(μ-O)Al(hfip)], with one Al cation tetra-hedrally coordinated by an oxido (O) anion, a hydroxido anion, and two hfip groups, whereas the second Al cation is coordinated by the oxido anion and three hfip groups.

3-Nitro-benzo-nitrile.

The crystal structure of 3-nitrobenzonitrile, CHNO, was elucidated by low-temperature single-crystal X-ray diffraction. The compound crystallizes in the Sohncke space group 2 and features two mol-ecules in the unit cell. Aromatic π-π stacking leads to stacks of mol-ecules in the [100] direction.

Hydrogen-Bonding Ability of Noyori-Ikariya Catalysts Enables Stereoselective Access to CF-Substituted -1,2-Diols via Dynamic Kinetic Resolution.

Stereopure CF-substituted -1,2-diols were prepared via the reductive dynamic kinetic resolution of the corresponding racemic α-hydroxyketones in HCOH/EtN. (Het)aryl, benzyl, vinyl, and alkyl ketones are tolerated, delivering products with ≥95% ee and ≥87:13 /. This methodology offers rapid access to stereopure bioactive molecules.

(1,2)-2-[()-2,2,2-Tri-fluoro-1-hy-droxy-eth-yl]-1-tetra-lol.

The crystal structure of the title enanti-opure tetralol derivative {systematic name: (1,2)-2-[()-2,2,2-tri-fluoro-1-hy-droxy-eth-yl]-1,2,3,4-tetra-hydro-naph-thalen-1-ol}, CHFO, synthesized by asymmetric transfer hydrogenation, was elucidated by low-temperature single-crystal X-ray diffraction. The enanti-opure compound crystallizes in the Sohncke space group 222 with one mol-ecule in the asymmetric unit and features intra-molecular as well as inter-molecular O-H⋯O hydrogen bonding. The absolute configuration was established from anomalous dispersion effects.

Tri-methyl-phosphine oxide dihydrate.

The title hydrate, MePO·2HO, crystallizes in the ortho-rhom-bic space group with eight formula units per unit cell. The extended structure displays O-H⋯O hydrogen bonding, with MePO mol-ecules as acceptors and water mol-ecules acting as donors and acceptors of hydrogen bonds, forming hydrogen-bonded layers, which propagate in the plane.

Crystal structure reinvestigation of silver(I) fluoride, AgF.

A crystal structure reinvestigation of AgF based on a low-temperature high-resolution single-crystal X-ray diffraction data is reported. Silver(I) fluoride crystallizes in the rock salt structure type ( ) with a unit-cell parameter of 4.92171 (14) Å at 100 K, resulting in an Ag-F bond length of 2.

()-2-[()-2,2,2-Tri-fluoro-1-hy-droxy-eth-yl]-1-tetra-lone.

The crystal structure of the title compound, CHFO, was elucidated by low-temperature single-crystal X-ray diffraction. The enanti-opure compound crystallizes in the Sohncke space group 2 and features one mol-ecule in the asymmetric unit. The structure displays inter-molecular O-H⋯O hydrogen bonding, which links the mol-ecules into infinite chains propagating parallel to [010].

Aqua-tri-fluorido-boron-1,3-dioxolan-2-one (1/2).

The crystal structure of the co-crystal of aqua-tri-fluorido-boron with two ethyl-ene carbonate (systematic name: 1,3-dioxolan-2-one) mol-ecules, BFHO·2OC(OCH), was determined by low-temperature single-crystal X-ray diffraction. The co-crystal crystallizes in the ortho-rhom-bic space group 222 with four formula units per unit cell. The asymmetric unit consists of an aqua-tri-fluorido-boron mol-ecule and two ethyl-ene carbonate mol-ecules, connected by O-H⋯O=C hydrogen bonds.

Nitro-sonium tetra-fluorido-borate, NOBF.

The crystal structure of oxido-nitro-gen(1+) tetra-fluorido-borate (nitro-sonium tetra-fluorido-borate), NOBF , was refined on the basis of single-crystal X-ray diffraction data at 150 K. The compound crystallizes in the baryte structure type with ortho-rhom-bic symmetry. The crystal structure exhibits cationic disorder with equal occupation of N and O atoms at the same site.

Catalytic Stereoconvergent Synthesis of Homochiral β-CF, β-SCF, and β-OCF Benzylic Alcohols.

We describe an efficient catalytic strategy for enantio- and diastereoselective synthesis of homochiral β-CF, β-SCF, and β-OCF benzylic alcohols. The approach is based on dynamic kinetic resolution (DKR) with Noyori-Ikariya asymmetric transfer hydrogenation leading to simultaneous construction of two contiguous stereogenic centers with up to 99.9% ee, up to 99.

On the Practical Applications of the Magnesium Fluorinated Alkoxyaluminate Electrolyte in Mg Battery Cells.

High-performance electrolytes are at the heart of magnesium battery development. Long-term stability along with the low potential difference between plating and stripping processes are needed to consider them for next-generation battery devices. Within this work, we perform an in-depth characterization of the novel Mg[Al(hfip)] salt in different glyme-based electrolytes.

Mixed Noble-Gas Compounds of Krypton(II) and Xenon(VI); [F Xe(FKrF)AsF ] and [F Xe(FKrF) AsF ].

The coordination chemistry of KrF has been limited in contrast with that of XeF , which exhibits a far richer coordination chemistry with main-group and transition-metal cations. In the present work, reactions of [XeF ][AsF ] with KrF in anhydrous HF solvent afforded [F Xe(FKrF)AsF ] and [F Xe(FKrF) AsF ], the first mixed krypton/xenon compounds. X-ray crystal structures and Raman spectra show the KrF ligands and [AsF ] anions are F-coordinated to the xenon atoms of the [XeF ] cations.

trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution.

A highly efficient enantio- and diastereoselective catalyzed asymmetric transfer hydrogenation via dynamic kinetic resolution (DKR-ATH) of α,β-dehydro-α-acetamido and α-acetamido benzocyclic ketones to ent- trans-β-amido alcohols is disclosed employing a new ansa-Ru(II) complex of an enantiomerically pure syn- N, N-ligand, i.e. ent- syn-ULTAM-(CH)Ph.

Manifestations of Weak O-H···F Hydrogen Bonding in M(HO) (BF) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg-Ba, Co, Ni, Zn).

Eight M(HO) (Z) salt hydrates were characterized by single-crystal X-ray diffraction (Z = BF): M = Ca, Sr, n = 7; M = Mg, Co, Ni, Zn, n = 6; M = Ba, n = 4, 5. Weak O-H···F hydrogen bonding between the M(HO) cations and Z resulted in room-temperature Fourier transform infrared (FTIR) spectra having sharp ν(OH) bands, with full widths at half max of 10-30 cm, which are much more narrow than ν(OH) bands in room temperature FTIR spectra of most salt hydrates. Clearly resolved ν(OH/OD) and ν(OH/OD) bands with Δν(OH) as small as 17 cm and Δν(OD) as small as 11 cm were observed (Δν(OX) = ν(OX) - ν(OX)).

Fluorinated reduced graphene oxide as a protective layer on the metallic lithium for application in the high energy batteries.

Metallic lithium is considered to be one of the most promising anode materials since it offers high volumetric and gravimetric energy densities when combined with high-voltage or high-capacity cathodes. However, the main impediment to the practical applications of metallic lithium is its unstable solid electrolyte interface (SEI), which results in constant lithium consumption for the formation of fresh SEI, together with lithium dendritic growth during electrochemical cycling. Here we present the electrochemical performance of a fluorinated reduced graphene oxide interlayer (FGI) on the metallic lithium surface, tested in lithium symmetrical cells and in combination with two different cathode materials.

Latent Porosity in Alkali-Metal MBF Salts: Structures and Rapid Room-Temperature Hydration/Dehydration Cycles.

Structures of the alkali-metal hydrates Li(HO)Z, LiK(HO)Z, Na(HO)Z, and Rb(HO)Z, unit cell parameters for RbZ and Rb(HO)Z, and the density functional theory (DFT)-optimized structures of KZ, K(HO)Z, RbZ, Rb(HO)Z, CsZ, and Cs(HO)Z are reported (Z = BF) and compared with previously reported X-ray structures of Na(HO)Z, K(HO)Z, and Cs(HO)Z. Unusually rapid room-temperature hydration/dehydration cycles of several MZ/M(HO)Z salt hydrate pairs, which were studied by isothermal gravimetry, are also reported. Finely ground samples of KZ, RbZ, and CsZ, which are not microporous, exhibited latent porosity by undergoing hydration at 24-25 °C in the presence of 18 Torr of HO(g) to K(HO)Z, Rb(HO)Z, and Cs(HO)Z in 18, 40, and 16 min, respectively.

Coordination of KrF to a Naked Metal Cation, Mg.

Examples of coordination compounds in which KrF functions as a ligand are very rare. In contrast, XeF provides a rich coordination chemistry with a variety of main-group and transition metal cations. The reactions of Mg(AsF ) and KrF in HF or BrF solvent have afforded [Mg(KrF ) (AsF ) ] and [Mg(KrF ) (AsF ) ]⋅2 BrF , respectively, the first examples of a metal cation ligated by KrF .

Hydroxylammonium Tetrafluoridooxidovanadate(V) - (NH3OH)[VOF4].

Hydroxylammonium tetrafluoridooxidovanadate(V) has been prepared by reaction of (NH3OH)Cl and VOF3 in anhydrous HF solvent and characterised in the solid state by single-crystal X-ray diffraction and Raman spectroscopy. Colourless (NH3OH)[VOF4] crystallises in the monoclinic P21/n space group with a = 7.2349(2) Å, b = 5.