Thermal properties of fluoride glasses and their gel precursors

Xerogels were prepared from zirconium, barium, aluminum, lanthanum and lithium acetates, corresponding to a Li containing ZBLA composition. The study of their thermal properties (DSC, TG/DTG, FT-IR) showed that they might be used as chemically stable precursors in the preparation of fluoride glasses. Hydrofluoric acid in solution was chosen as a mild fluorinating agent. This newly proposed technique of fluorinating allowed to obtain high quality ZBLALi glass which presents the advantage of higher thermal stability and homogeneity in comparison with the glass obtained using individual commercial fluorides.This revised version was published online in November 2005 with corrections to the Cover Date.     

氟化钾负载改性法制备碱性NaY沸石

氟化钾（ＫＦ）可以高度分散于八面沸石表面，通过与ＮａＹ沸石表面发生相互作用产生ＫＯＨ类碱物种，使ＫＦ／ＮａＹ具有类似于ＫＯＨ／ＮａＹ的碱性，在异丙醇探针反应的碱性催化活性也与ＫＯＨ／ＮａＹ相似，由于沸石中的Ｓｉ组分容易与ＫＯＨ生成强度低的碱性化合物，妨碍ＫＦ或ＫＯＨ负载过程中强碱位的生成，因此ＫＦ／ＮａＹ的碱强度介于ＫＦ／ＳｉＯ２和ＫＦ／γ－Ａｌ２Ｏ３之间。     

Fluoride and lead adsorption on carbon nanotubes

The properties and applications of CNT have been studied extensively since Iijima discovered them in 1991[1,2]. They have exceptional mechanical properties and unique electrical property, highly chemical stability and large specific surface area. Thus far, they have widely potential applications in many fields. They can be used as reinforcing materials in composites[3], field emissions[4], hydrogen storage[5], nanoelectronic components[6], catalyst supports[7], adsorption material and so on.…     

One-pot synthesis of 1-aryl-3-methyl-1,3-dienes using methallyl(trimethyl)silane and aldehydes and their low temperature (Z)→(E) isomerization induced by sulfur dioxide

2-Methylprop-2-ene-1-sulfonyl fluorides can be easily prepared via the ene reaction of methallylsilanes and SO₂. In the presence of a base, aldehydes and 2-methylprop-2-ene-1-sulfonyl fluorides give 1,3-(E) and (Z)-dienes. Their (Z)→(E) isomerization by classical means fails or leads to their polymerization. It is shown that SO₂ can isomerize 1-aryl-3-methyl-1,3-dienes at low temperature, without formation of sulfolenes (cheletropic addition/elimination). Preliminary mechanistic studies suggest that SO₂ adds to 1,3-dienes forming 1,4-diradical intermediates that are responsible for the (Z)→(E) isomerizations.     

The effect of pressure on the dissociation constant of hydrofluoric acid and the association constant of the NaF ion pair at 25°C

The effect of pressure on the dissociation constant of hydrofluoric acid was determined by using the indicator technique at 25°C at an ionic strength of 0.1m over a pressure range of 1 to 2000 atm. A value of 3.14 for pK _a ^* at I =0 was obtained by extrapolation to zero ionic strength at 1 atm. The pressure dependence yielded a partial molar volume change of –9.6 cm³-mol^–1 and a compressibility change of — 35×10^–3 cm³-mol^–1 –atm^–1 for the dissociation. The dependence of ionic strength on the association constant K _A ^* of NaF was studied at 25°C and 1 atm. Extrapolation to I=0 yielded a pK _A ^* of –0.78. The pressure dependence of K _A ^* gave a change of volume of 3.26 cm³-mol^–1 and a change in compressibility of 6×10^–3 cm³-mol^–1-atm^–1 for the formation of the ion pair.     

Crystal structure of tetraethylammonium fluoride-water (4/11), 4(C2H5)4N+F− · 11H2O,a clathrate hydrate containing linear chains of edge-sharing (H2O)4F− tetrahedra and bridging water molecules

Crystals of 4(C₂H₅)₄N⁺F^– · 11H₂O are orthorhombic, space groupPna2₁, witha=16.130(3),b=16.949(7),c=17.493(7) Å, andZ=4. The structure was shown to be a clathrate hydrate containing infinite chains of edge-sharing (H₂O)₄F^– tetrahedra extending parallel to thea axis. The chains are laterally linked by bridging water molecules to form a three-dimensional hydrogen-bonded anion/water framework. The ordered (C₂H₅)₄N⁺ cations occupy the voids in two open channel systems running in theb andc directions. FinalR _F =0.091 for 2278 observed MoK data measured at 22°C. Supplementary Data: relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82010 (20 pages).Dedicated to Professor H. M. Powell.     

CONTRIBUTION OF MACROSCOPIC DIMENSION EFFECT TO PIEZOELFCTRICITY IN POLYVINYLIDENE FLUORIDE

In this paper, we have studied the piezoelectricity in the poled uniaxially drawn polyvinylidene fluoride. The piezoelectric constants d_(31), d_(32), d_(33)~αand Young's moduli 1/s_11 and 1/s_(22) have been determined as a function of the remanent polarization Pr. The piezoelectric constants of the samples show a strong in-plane anisotropy. Such an anisotropy is mostly attributable to different Poisson's ratio. It is found that the piezoelectric activity mainly arises from macroscopic dimensional change.     

SbF5/PAF—a novel fluorinating reagent in preparing fluorine compounds

A novel fluorination reagent and catalyst, SbF₅/PAF (porous aluminum fluoride), was prepared by impregnating SbCl₅ into PAF and then treating with anhydrous hydrogen fluoride. The prepared reagent had an excellent catalytic activity in halogen-exchange, and also improved the properties of SbF₅, such as hydroscopicity, corrosion, and toxicity. SbF₅/PAF was successfully used in organic synthesis as a fluorinating reagent, and a fixed bed catalyst for F/Cl exchange.     

Competitive demethylation and substitution in N,N,N-trimethylanilinium fluorides

Fluorination of aromatic compounds by nucleophilic displacement of trimethylanilinium salts by fluoride is a commonly used reaction for radiotracer synthesis. Though the liberated trimethylamine is thought to be an excellent leaving group for this type of S_NAr reaction, scattered reports show that amine demethylation (reverse Menschutkin reaction) sometimes dominates over substitution, particularly when relatively electron rich fluoroarenes are the desired targets. Here we provide systematic experimental and theoretical studies of trimethylanilinium demethylation and substitution. Results from these studies highlight the limits of this leaving group in fluoroarene synthesis and have important ramifications for the design of nucleophilic fluorinating agents featuring ammonium cations.     

Study of Redox-induced Reactions of Vinylidene and bis-Vinylidene Complexes of Manganese

Oxidative dehydrodimerization of some phenylvinylidene complexes of manganese is studied by cyclic voltammetry. In the case of (⁵-C₅H₅)(CO)₂Mn=C=C(H)Ph, the process occurs as the homolysis of the C–H bond in the radical cation of {(⁵-C₅H₅)(CO)₂Mn=C=C(H)Ph}^+· and the dimerization of intermediate -phenylethinyl cation [(⁵-C₅H₅)(CO)₂Mn–CC–Ph]⁺ to a binuclear dication of bis-carbine type (⁵-C₅H₅)(CO)₂Mn⁺C– C(Ph)=C(Ph)–CMn⁺(CO)₂(⁵-C₅H₅). The reduction of the latter leads to binuclear bis-vinylidene complex (⁵-C₅H₅)(CO)₂Mn=C=C(Ph)–C(Ph)=C=Mn(CO)₂(⁵-C₅H₅). Oxidative dehydrodimerization of complexes (⁵-C₅R₅)(CO)(L)Mn=C=C(H)Ph (R = H, L = PPh₃; R = Me, L = CO) occurs through the immediate C–C coupling of radical cations {(⁵-C₅R₅)(CO)(L)Mn=C=C(H)Ph}^+· and yields binuclear dication bis-carbine complexes (⁵-C₅R₅)(CO)(L)Mn⁺C–C(H)(Ph)–C(H)(Ph)–CMn⁺(CO)(L)(⁵-C₅R₅), whose reduction leads to neutral compounds (⁵-C₅H₅)(CO)₂Mn=C=C(Ph)–C(Ph)=C=Mn(CO)(L)(⁵-C₅H₅). Complex (⁵-C₅H₅)(CO)₂Mn=C=C(Ph)–C(Ph)=C=Mn(CO)₂(⁵-C₅H₅) undergoes the oxidation-induced nucleophilic addition of water, forming cyclic bis-carbene product with a bridge heterocyclic ligand (-3,4-diphenyl-2,5-dihydro-2,5-diylidene)-bis-(⁵-cyclopentadienyldicarbonyl manganese).