Inversion of ν(MHal) stretching frequencies in the spectra of dihalosilylenes, -germylenes, -stannylenes,and their complexes with Lewis bases

The vibrational spectra of tetravalent metal halides (M = Si, Ge, Sn) and the corresponding dihalocarbene analogs M^IIHal₂, obtained by the authors, and the relevant published data are compared. The spectra of the M^IIHal₂ species exhibit inversion of the M-Hal stretching frequencies (ν^s(M^IIHal) > ν ^as(M^IIHal)). This can be used for analytical purposes and allows one to distinguish between the spectra of the M^IV and M^II halides. The IR and Raman spectra of the complexes of dihalogermylenes and -stannylenes with triphenylphosphine and 1,4-dioxane also exhibit inversion of the ν(MHal) stretching frequencies. This confirms the conclusion drawn earlier based on the analysis of the geometric parameters and reactivities of the complexes in question that the divalent state of the M atom in these species is retained. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1089–1092, May, 2005.     

Pre-irradiation induced grafting of styrene into crosslinked and non-crosslinked polytetrafluoroethylene films for polymer electrolyte fuel cell applications. II: Characterization of the styrene grafted films

Crosslinked and non-crosslinked polytetrafluoroethylene films (RX-PTFE and V-PTFE films, respectively) were irradiated by γ-ray and then grafted with styrene in liquid phase. Microscope FT-IR spectroscopy, TGA, solid state ¹³C CP/MAS and high resolution HS/MAS NMR spectroscopy, wide-angle X-ray diffraction (WAXD) study were used to get the structural information of the styrene grafted RX-PTFE and V-PTFE films. From microscope FT-IR spectra of the grafted RX-PTFE films, the “grafting front mechanism” was proved. TGA analysis showed that the grafted films have a small degradation step and two main degradation steps. In the ¹³C CP/MAS NMR spectra of the non-grafted films, there are no signal due to the absence of the hydrogen atom. While in the spectra of the grafted films, there are signals attributed to the polystyrene grafts. In the ¹³C HS/MAS NMR spectra of the grafted films, the relative intensity of the peaks attributed to the polystyrene grafts increased while the relative intensity of the peak attributed to PTFE matrix decreased with the increase in the DOG. From WAXD patterns, the intensity of the crystalline peak decrease with the increase in the DOG. The grafted films were sulfonated by chlorosulfonic acid and the results of highest IEC value exceeded 3.0. Those results will be reported in the near future.     

On the Nonlocal Electron Kinetics in s- and p-Striations of DC Glow Discharge Plasmas: I. Electron Establishment in Striation-like Fields

The nonlocal behavior of the electrons in strongly modulated and period-averaged electric fields typical of s- and p-striations in neon glow discharge plasmas is investigated by numerically solving the axially inhomogeneous electron Boltzmann equation. A good agreement between the period lengths measured in the striations and those obtained from the spatially periodic electron relaxation in the period-averaged field of the striations is found confirming the close relation of both phenomena. The s- and p-striations represent the fundamental and first harmonics of the inherent periodic electron relaxation. Furthermore, starting from different boundary conditions the establishment of the velocity distribution function and of selected macroscopic quantities of the electrons into unique periodic states under the action of strongly modulated striation-like fields is investigated. It is shown that the same damping processes that cause in homogeneous fields a relaxation into homogeneous states lead to unique periodic states in strongly modulated fields.     

Einfache Trithio- und Perthiocarbonatokomplexe mit interessanter Koordinationschemie: [E(CS3)2]2− (E = Sn,Zn, Cd), [E(CS3)3]3− (E = As,Sb, Bi,Co), {Cu(CS3)−}∞ und [Zn(CS4)2]2−

Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS₃)₂]^2? (E = Sn, Zn, Cd), [E(CS₃)₃]^3? (E = As, Sb, Bi, Co), {Cu(CS₃)^?}_∞ and [Zn(CS₄)₂]^2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh₄)₂[Zn(CS₃)₂] ( 2 ), (PPh₄)₂[Cd(CS₃)₂] ( 3 ), (PPh₄)₂[Sn(CS₃)₂] ( 4 ), (PPh₄)₃[As(CS₃)₃] ( 5 ), (PPh₄)₃[Sb(CS₃)₃] ( 6 ), (PPh₄)₃[Bi(CS₃)₃] ( 7 ), (PPh₄)₃[Co(CS₃)₃] ( 8 ) and (PPh₄)Cu(CS₃) ( 9 ) have been isolated. (PPh₄)₂[Zn(CS₄)₂] · CH₃NO₂ ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh₄)₂[C₂S₆] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, ¹¹³Cd/⁵⁹Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht.     

Determining the chromophore in the amylopectin–iodine complex by theoretical and experimental studies

A partial hydrolysis of amylose followed by the addition of iodine provides a spectrum almost identical to that of the amylopectin–iodine (API) complex suggesting the involvement of smaller “amylose-like” units in the API complex. Our theoretical studies on different polyiodine and polyiodide species suggest that a nearly linear I₄ unit stabilized within the cavity of a small “amylose-like” helix is responsible for the characteristic API spectrum. Since there are 2.75 anhydroglucose residues (AGU) for every iodine atom in the amylose–iodine (AI) complex and a structural similarity exists between the API and the AI (amylose–iodine) complexes, we identify (C₆H₁₀O₅)₁₁I₄ to be the chromophore in the API complex. © 1994 John Wiley & Sons, Inc.     

Use of intermittent jets to enhance flux in crossflow filtration

This paper deals with the influence of a new flow unsteadiness on the permeate fluxes in crossflow filtration. A pneumatically controlled valve generates intermittent jets from the main flow, causing the formation of large vortices moving downstream along the tubular membrane. The main results of the numerical calculation of such flows are given. The experimental study was carried out by filtering a bentonite suspension through an ultrafiltration mineral membrane. Time evolutions of flux were achieved in steady and unsteady operating conditions. Results concerning the influence and limits of the nozzle to tube diameter ratio and the jet velocities are discussed. The applicability of such an unsteady flow is examined with a view to effects on energy consumption and possible viscosity effects.     

Structure formation in heavy metal oxyhydrates at low rates of gel formation

Oxyhydrate gels have a hydrophilic surface, due to which they undergo destruction and secondary polymerization in aqueous media. Prolonged storage in aqueous solution gives rise to regions with selfsimilar helical ordering in gels. Structuring of this kind is also observed when synthesis is conducted under conditions that provide low gelation rates. Electromagnetic UV and visible radiation is another means to change the gel structure; it makes the oligomer species pass into the excited state, due to which one of the directions of structuring becomes dominant. This work summarizes the results of computer simulation of gel agglomerates. For oxyhydrate systems, helical ordering was found to be one of the local energy minima. The units of a macrohelix can lie at various angles relative to one another, and they can change, after absorption of energy, the helix pitch and the order of elements in the helix.     

Calculation of harmonic force constants,vibrational frequencies and integrated intensities of some organic molecules using the MINDO—Forces method

The harmonic force constants, vibrational frequencies and integrated intensity ratios of CH₂, H₂O, CH₂O, C₂H₂, CO₂, HCN, CH₃, CH₄, and C₂H₄ have been calculated using the MINDO—FORCES program and the Pulay method for the calculation of the molecular force constants. The results obtained are in general quite satisfactory when compared with available literature values. The results are, however, not as satisfactory in case of molecules containing heteroatoms, due to the neglect of some dipolar repulsion integrals for the heteroatoms by the MINDO/3 method. Calculated integrated intensities for CH₃ and C₂H₄ agree well with experimental results. The calculated integrated intensities for other molecules are obtained for the first time and no comparison with published data is therefore possible.Part of the M.Sc. Thesis of K. H. A. 1978.     

碱性介质中二(碲酸根)合铜(Ⅲ)酸根氧化乙二醇一乙醚的反应动力学及机理

在碱性介质中用分光光度法研究了二过碲酸合铜(Ⅲ)配离子(DTC)氧化乙二醇一乙醚(EGE)的反应动力学及机理。反应速率表明:反应对DTC为准一级,对EGE为分数级;在保持准一级条件([EGE]》[DTC])下,表观速率常数随着OH^-浓度的增加而增大,随着TeO₄^2-浓度的增加而减小;有负的盐效应。据此提出了包括配离子和EGE形成络合物的前期平衡的反应机理,由假设反应机理推出的速率方程能很好的解释全部实验现象,进一步求得速控步的速率常数和活化     

Assembled catalyst of palladium and non-cross-linked amphiphilic polymer ligand for the efficient heterogeneous Heck reaction

The efficient heterogeneous Heck reaction was achieved by a new networked and supramolecular catalyst PdAS-V (1b). Employing of PdAS-V in 5.0×10⁻⁵ mol equiv. efficiently progressed the heterogeneous Heck reaction of a series of aryl iodides with acrylates, styrenes and acrylic acid. PdAS-V was successfully recycled five times without any decrease in its activity, and showed good stability in toluene and water, and hence the Heck reaction was efficiently performed in both reaction media. The use of 8.0×10⁻⁷ mol equiv. of PdAS-V resulted in the coupling product in 92% yield with the turnover number (TON) and the turnover frequency (TOF) of PdAS-V reached up to 1,150,000 and 12,000, respectively. The efficient synthesis of resveratrol was achieved via the PdAS-V-promoted Heck reaction.