Syntheses,Crystal Structure and Reactivity of Tin(II) Bis[N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide]

Metallation of N‐(diphenylphosphanyl)(2‐pyridylmethyl)amine with n‐butyllithium in toluene yields lithium N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide ( 1 ), which crystallizes as a tetramer. Transamination of N‐(diphenylphosphanyl)(2‐pyridylmethyl)amine with an equimolar amount of Sn[N(SiMe₃)₂]₂ leads to the formation of monomeric bis(trimethylsilyl)amido tin(II) N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide ( 2 ). The addition of another equivalent of N‐(diphenylphosphanyl)(2‐pyridylmethyl)amine gives homoleptic tin(II) bis[N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide] ( 3 ). In these complexes the N‐(diphenylphosphanyl)(2‐pyridylmethyl)amido groups act as bidentate bases through the nitrogen bases. At elevated temperatures HN(SiMe₃)₂ is liberated from bis(trimethylsilyl)amido tin(II) N‐(diphenylphosphanyl)(2‐pyridylmethyl)amide ( 2 ) yielding mononuclear tin(II) 1,2‐dipyridyl‐1,2‐bis(diphenylphosphanylamido)ethane ( 4 ) through a C–C coupling reaction. The three‐coordinate tin(II) atoms of 2 and 4 adopt trigonal pyramidal coordination spheres.     

Implementation of the diagonalization‐free algorithm in the self‐consistent field procedure within the four‐component relativistic scheme

A recently developed Thouless‐expansion‐based diagonalization‐free approach for improving the efficiency of self‐consistent field (SCF) methods (Noga and ?imunek, J. Chem. Theory Comput. 2010, 6, 2706) has been adapted to the four‐component relativistic scheme and implemented within the program package ReSpect. In addition to the implementation, the method has been thoroughly analyzed, particularly with respect to cases for which it is difficult or computationally expensive to find a good initial guess. Based on this analysis, several modifications of the original algorithm, refining its stability and efficiency, are proposed. To demonstrate the robustness and efficiency of the improved algorithm, we present the results of four‐component diagonalization‐free SCF calculations on several heavy‐metal complexes, the largest of which contains more than 80 atoms (about 6000 4‐spinor basis functions). The diagonalization‐free procedure is about twice as fast as the corresponding diagonalization. © 2014 Wiley Periodicals, Inc.     

Study of atmospheric pressure chemical ionization of PETN by ion mobility spectrometry/tandem mass spectrometry

We present the results of studying the effects of temperature and humidity of the reaction medium and the intensity of ultraviolet radiation on the atmospheric pressure chemical ionization of Penthrite. The peculiarities of the ion mobility spectra of this compound obtained by ion mobility spectrometry-tandem mass spectrometry are analyzed.     

Shear Stability of Highly Concentrated Emulsions

Shear stability of water-in-oil highly concentrated emulsions was characterized by the rate of the droplet size decrease at a constant shear rate. Samples of different concentration (ranging from 0.85 to 0.94 wt %), prepared with different surfactants and three types of oils were analysed. The emulsions under study are visco-plastic media with a clearly expressed yield stress. The usually used Capillary number is not valid for such systems but instead Bingham number (ratio of the yield stress to interfacial forces) was used to characterise their stability. Within the frames of our experiment, it has been proven that the correlation between shear stability of emulsions and the Bingham number exists.     

Superhyperfine structure in the EPR spectra and optical spectra of impurity f ions in dielectric crystals: A review

The results of observation and simulation of the superhyperfine (ligand hyperfine) structure (SHFS) of the electron paramagnetic resonance (EPR) spectra of rare-earth and uranium impurity ions in dielectric crystals have been systematized. The resolved SHFS of the EPR spectra of doped cubic crystals (with the fluorite and perovskite structures) has been observed for orientations of a constant magnetic field along the crystallographic axes. Most attention has been paid to tetragonal double fluorides LiRF₄ (R = Y, Lu, Tm), in which the SHFS of the EPR spectra has also been found for intermediate orientations of the magnetic field. For the LiYF₄: Nd³⁺ single crystal, the splitting of optical spectral lines due to the interaction of Nd³⁺ ions with nuclear magnetic moments of the nearest neighbor fluorine ions has been observed for the first time. The Van Vleck paramagnet LiTmF₄: U³⁺ is characterized by the SHFS with clearly distinguishable components due to the interaction of uranium ions both with nuclei of the fluorine ions and with enhanced magnetic moments of the thulium nuclei. The SHFS envelopes of the EPR spectra of Yb³⁺, Ce³⁺, Nd³⁺, and U³⁺ ions in LiYF₄ and LiLuF₄ crystals are well reproduced by numerical calculations based on the microscopic model using only three fitting parameters: the width of transitions between the electron-nuclear sublevels of the complex containing the paramagnetic ion and nuclei of the ligands and two constants of covalent bonding of the f electrons with 2s and 2p electrons of the nearest neighbor fluorine ions.     

Rheological properties of road bitumens modified with polymer and solid nanosized additives

The study of the viscoelastic properties of composites based on road bitumens have shown that the addition of polymeric modifiers (poly(bytadiene-block-styrene) or devulcanized rubber particles) substantially increases the storage and loss moduli and decreases the intensity of reduction in the storage modulus with temperature by several orders of magnitude. However, at high polymer content, growth inadmissible from the point of view of acceptable technological parameters is observed in the apparent viscosity. The introduction of carbon nanotubes into bitumen does not substantially affect its viscoelastic properties. Filling with meta-kaolin promotes an increase in the storage modulus at elevated temperatures. It has been shown that a direct correlation may be established between the objective characteristics of bitumen-based composites and standard specification parameters, such as penetration depth and heat resistance.