Über die Gasphasenstruktur von CF3NCl2 und die Darstellung von CF3NCl2F+MF6− (M = As,Sb) und CF2 = NClF+SbF6−

Gas Phase Structure of CF₃NCl₂ and Preparation of CF₃NCl₂F⁺MF₆^? (M = As, Sb) and CF₂ = NCl₂F⁺SbF₆^? The gas phase structure of CF₃NCl₂ is reported. The following skeletal parameters are derived (r_a-values, error limits are 3σ values): N? C = 1.470(6) Å, N? Cl = 1.733(3) Å, ClNCl = 111.5(4)° and ClNC = 107.6(5)°. CF₃NCl₂F⁺MF₆^? is prepared by fluorination of CF₃NCl₂ with XeF⁺MF₆^?. The same educt CF₃NCl₂ reacts with XeF⁺SbF₆^? at ?40°C to CF₂ = NClF⁺SbF₆^? under elimination of ClF.     

IR Spectroscopic Study of the Interaction of Transition Metal Ions with Hydroxyapatite Modified by Potassium Ferrocyanide

IR spectroscopy was used to study the modification of hydroxyapatite by potassium ferrocyanide and the interaction of transition metal ions with the modified adsorbent. The structural changes of hydroxyapatite upon the adsorption of Zn²⁺ ions were studied by X-ray phase analysis. Potassium ferrocyanide was found to interact with the surface hydroxyl groups of hydroxyapatite through the nitrogen unshared electron pair. Co²⁺, Ni²⁺, and Zn²⁺ ions were found to eliminate outer-sphere K⁺ ions of adsorbed ferrocyanide to give Fe²⁺— CN—M²⁺— NC—Fe²⁺ bridging structures. Zn²⁺ cations additionally eliminate a part of the Ca²⁺ ions from structural positions of hydroxyapatite, which leads to the appearance of a two-phase hydroxyapatite–sholzite system with heterogeneous distribution of the Ca²⁺ ions in the mot her mineral phase, while the Zr²⁺ ions are found in the new sholzite phase.     

Ionization potentials of non-metal monosulfides. Conjugation in radical cations containing Group IV elements

The first vertical ionization potentialsI(n_s) of 69 monosulfides XSY (X, Y=H, Hal, organic, or heteroorganic substituent) are related to the inductive σ_I resonance (σ _R ⁺ ) and polarizability (σ_α) constants of the substituents by dependences of theI(n_S)=a+bΣσ_I+bΣσ_R+bΣσ_α type. TheI(n_s) values are also affected by hyperconjugation which increases on going from XSH to XSY (Y≠H) compounds. The first calculations of the σ _R ⁺ parameters characterizing the conjugation of Si-, Ge-, Sn-, and Pb-containing substituents with the S^.+ radical cation center are reported. The reasons for weakening of resonance donor properties of heteroorganic substituents of the +M-type in the systems studied as compared to those of the same substituents in the corresponding aromatic radical cations are considered. Translated fromIzvestiya Akademii Nauk. Seriya Khmicheskaya, No. 1, pp. 25–31, January, 2000.     

Gas-phase polar [4+ + 2] cycloaddition with ethyl vinyl ether: a structurally diagnostic ion-molecule reaction for 2-azabutadienyl cations

The intrinsic reactivity of eight gaseous, mass-selected 2-azabutadienyl cations toward polar [4(+) + 2] cycloaddition with ethyl vinyl ether has been investigated by pentaquadrupole mass spectrometric experiments. Cycloaddition occurs readily for all the ions and, with the only exception of those from the N-acyl 2-azabutadienyl cations (N-acyliminium ions), the cycloadducts are found to dissociate readily upon collision activation (CID) both by retro-Diels-Alder reaction and by a characteristic loss of an ethanol (46u) neutral molecule. Ethanol loss from the intact polar [4(+) + 2] cycloadduct functions therefore as a structurally diagnostic test: 72 u neutral gain followed by 46 u neutral loss, i.e., as a combined ion-molecule reaction plus CID 'signature' for N-H, N-alkyl and N-aryl 2-azabutadienyl cations. The two N-acyliminium ions tested are exceptional as they form intact cycloadducts with ethyl vinyl ether which dissociate exclusively by the retro-Diels-Alder pathway.     

Piperazine quaternary diammonium salts as additives to background electrolytes in capillary zone electrophoresis

The differential behavior of five different quaternary mono- and diammonium salts, among the 18 investigated, in modulating the electroendoosmotic flow (EOF) and analyte separations in capillary zone electrophoresis is evaluated. It is found that quaternary diammonium salts with positive charges separated by more than four carbon atoms, while exhibiting a very strong affinity for chromatographic silica beads, to the point of exhibiting Rf values close to zero, display, on the contrary, a very poor affinity for the silica wall of capillaries. Compounds separated only by a C2 unit (i.e., 1,4-dialkyl-1,4-diazoniabicyclo[2,2,2,]octane, salts 17 and 18) show high Rf values due to strong ion pair association. The unique behavior of quaternary monoammonium salts possessing an iodinated alkyl (butyl or octyl) tail (i.e., 1, 6, and 7) is attributed to their ability to be covalently affixed to the silica wall via alkylation of ionized silanols at alkaline pH values. They thus strongly modulate and typically invert the EOF, even when not present in the background electrolyte. On the contrary, all diammonium salts, devoid of such alkyl tails, are unable to modulate the EOF and to prevent analyte binding to the silica wall, since they are rapidly removed from the wall by the voltage gradient. However, if added in small amount to the background electrolyte, they offer excellent separations of mixtures of very similar organic acids and prevent any interaction with the capillary wall.     

Synthesis and Properties of 1,3,5-Tris(phenoxymethyl)-2,4,6-triethylbenzenes as NH 4 + Ionophores

The synthesis, spectroscopic characterization, and potentiometricmeasurements of new 1,3,5-trisphenoxy-2,4,6-triethylbenzenesare described. The cation binding abilities oftrisphenoxy-2,4,6-triethylbenzenes were strongly dependenton the substituents introduced on the phenoxy units: thereceptors with electron-donating alkoxy groups (–OCH₃and –OCH₂C₆H₅) provided similar potentiometricperformance to that of nonactin in PVC-based, ion-selectivemembrane electrodes. The trisphenoxy-2,4,6-triethylbenzenereceptors with ether groups on ortho and meta positions ofphenoxy units exhibit almost identical cation recognitionproperties in the PVC membranes. It is postulated that theelectron-donating nature of the alkoxy substituents increases theelectron density in the phenoxy units, resulting in increasedcation- interactions.     

Ab Initio Construction of Quasiadiabatic Potential-Energy Surfaces for Cycloaddition Reactions of Ethene and Substituted Allylic Cations

The nature of some well known 2π + 2π cycloaddition reactions was studied by explicit construction of the quasiadiabatic potential-energy surfaces for the cycloaddition of ethene and various monosubstituted allylic cations. Such surfaces determined by ab initio MO computations are particularly suitable for analysis of symmetry selection rules. By examining the characteristics of such surfaces, we have studied the substituent effect and the role played by the positive charge in such systems. Qualitative discussion based on simplified MO, involving fewer electrons, is also given.     

The pKR+ values for coordinated propargyl cations [Cp2M2(CO)4(μ-η2,η3-HC≡CCR1R2)]+ (M = Mo,W)

The pK_R+ values for metal-stabilized carbocations [Cp₂M₂(CO)₄(-²,³-HCCCR¹R²)]⁺ (M = Mo, W) containing primary (R¹ = R² = H), secondary (R¹ = H, R² = Me), or tertiary (R¹ = R² = Me) coordinated propargyl cations were measured in 50% aqueous acetonitrile. Their stability increases from the tertiary to primary cation, and the stability of the tungsten-containing cations is higher than that of the corresponding molybdenum analogs.     

A study on the mechanism of dissolution of the cellulose/NH3/NH4SCN system. I

Ammonia/ammonium thiocyanate (NH₃/NH₄SCN) is an excellent swelling agent and solvent for cellulose, even at a high degree of polymerization. Because polymorphic conversion in cellulose has been a long-standing, perplexing, troublesome problem, we have undertaken to study that mechanism. Solid state CP/MAS ¹³C-NMR and X-ray analysis proved to be very useful analytical techniques for the task. It appears that during temperature cycling, specific cellulosic inter- and intramolecular hydrogen-bonds are broken as polymorphic conversion proceeds sequentially from the polymorph I to III, and finally at total solvation to amorphous. This proceeds correspondingly via transformation of the polymorph conformations of CH₂OH from trans-gauche, “tg,” to gauche-trans, “gt,” to gauche-gauche, “gg.” © 1994 John Wiley & Sons, Inc.     

Phase changes in the syrian phosphorite–ammonium sulphate system

With a complex of physico-chemical methods for analysis it is proved that in the course of mechanochemical treatment of a Syrian phosphorite and ammonium sulphate mixture new phases have been formed. The thermal analysis proves an increase in the reaction properties of the ammonium sulphate and the Syrian phosphorite which is a prerequisite for the increase in the content of P₂O₅^assimilated , in the activated phosphorite mixtures and the possibility to use them in the production of NP complex fertilizers.