Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

Solid state a.c. conductivity and FT-IR spectral analyses for the conflicting effects of proton mobility and association in some azophenol derivatives of cyclic phosphazene

Variable strength H-bonding affects the mobility and so electric conduction of protons differently. Also, variable extent mesomerism modifies electric conduction with varying dielectric features. Both these molecular modifiers are properly cited using azophenol derivatives as model compounds for discussion of their consequences in the varying features of electric conduction. The electric permittivity shows low-frequency dispersion characteristic of ionic conduction over mobile charge carries; the mobility shifts at a critical temperature T _c, being structure dependent. The frequency-dependent Z′′-Z′ layout changes with temperature from linear at low temperatures to semicircular above T _c within a frame of temperature-sensitive dipole-ionic mediated conduction. The a.c. conductivity, σ_ac, increases with frequency and temperature and becomes frequency insensitive, like d.c. conductivity, σ_dc, above the T _c because of the escalating contribution from the d.c. conduction. The mesomeric structure seems to prompt a dipole-based electric conduction of high relaxation energy over the strongly associated phenolic protons that may be thermally activated above the T _c into a much lower relaxation energy protonic conduction of up to two orders higher conductivity. The protonic conduction emerges at a T _c that falls with a drop in the relaxation energy following a similar order of increasing proton mobility and mesomerism in the azophenol derivatives: azocatechol>azoquinol>azoresorcinol. On the molecular level, variable temperature infrared spectroscopy reveals higher proton mobility and mesomerism for the azocatechol derivative that demonstrates its higher protonic conductivity at lower T _c and relaxation energy, compared to the azoquinol and azoresorcinol derivatives. This is well verified in the light of conflicting intramolecular H-bonding that assists the proton mobility in azocatechol whereas it associates the protons in azoresorcinol more than in azoquinol. Electronic Publication     

Towards insight into properties and stabilities of complexes of ozone with CO2, CS2 and SCO species

The MP2 method in combination with the aug-cc-pVXZ (X = D and T) basis set has been carried out to examine the complexes between O₃ and isostructure species of CO₂, CS₂ and SCO. Two, two and four minima have been located on the potential energy surfaces of O₃–CO₂, O₃–CS₂ and O₃–SCO complexes, respectively. The results reveal that the stabilization of complexes should be in the order O₃–CS₂ > O₃–SCO > O₃–CO₂.     

Simultaneous Spectrophotometric Determination of Zinc and Nickel in Water Samples by Mean Centering of Ratio Kinetic Profiles

The mean centering of ratio kinetic profiles method was used for the simultaneous determination of binary mixtures of Ni(II) and Zn(II) in water samples, without prior separation steps. The method is based on the difference in the rate of the reaction of Ni(II) and Zn(II) with xylenol orange at pH 5.3. The method allows rapid and accurate determination of Ni(II) and Zn(II). The analytical characteristics of the methods for the simultaneous determination of binary mixtures of Ni(II) and Zn(II) were calculated. The linear range was 0.025‐2.400 μg mL^?1 and 0.025‐2.20 μg mL^?1 for Zn(II) and Ni(II), respectively. Interference effects of common anions and cations were studied, and the method was successfully applied to the simultaneous determination of Zn(II) and Ni(II) in water samples.     

On designing experiments for a dynamic response modeled by regression splines

Dynamic response systems are often found in science, engineering, and medical applications, but the discussion on experimental design for such a system is relatively rare in literature. For an experimenter, designing such experiments requires making decisions on (1) when or where to take response measurements along the dynamic variable and (2) how to choose the combination of experimental factors and their levels. The first consideration is unique for such experiments, especially when the measurement cost is high. In this paper, we present a design approach through the mixed‐effect linear model, which is based on a hierarchical B‐spline function for the dynamic response. We develop several theorems that can assist in finding a statistically efficient sampling plan and propose an algorithm for searching the D‐optimal design of a dynamic response system.     

Synthesis and Characterization of Soluble Polyester Based on Calixarene Dicarboxylic Acid with Tertiary Butyl Pendant Groups

A series of new polycalixesters(PCES) were synthesized by polyesterification of calixarene dicarboxylic acid derivatives having tertiary butyl pendant groups at the upper rim using five different diols. All polyesters were readily soluble in polar solvents such as NMP(N-methylpyrrolidone), DMF(dimethylformamide), DMSO(dimethylsulfoxide), pyridine, THF(tetrahydrofurane), HMPA(hexamethylenephosphoramide) and DMAC(dimethylacetamide). The PCES were also partially soluble in TCE(tetrachloroethane) and ethanol and they were unsoluble in aceton. The glass transition temperatures of polyesters were between 80-184 °C, the crystallinity temperatures of polyesters were between 130–212 °C and the melting temperatures of polyesters were between 185–234 °C, as determined by differential scanning calorimeter(DSC). The inherent viscosities of polyesters were obtained from 0.55 dL/mg to 0.61 dL/mg. The temperatures at 10% weight loss of polyesters ranged from 182 °C to 237 °C. The temperatures at 25% weight loss of polyesters ranged from 258 °C to 331 °C. The half weight loss(50%) temperatures of polyesters were among 315 °C to 371 °C and the char yields at 600 °C were determined within 13% to 22.3% in N2 atmosphere, as determined by thermo gravimetric analysis(TGA). The polyester, PES3, has the higher melting point(234 °C) and higher inherent viscosity(molecular weight) than the other polyesters.     

Computational study on the multi-channel mechanism of disulfur and ozone reaction

Structural Chemistry - The reaction mechanism of disulfur (S2) and O3 on the triplet and singlet potential energy surfaces has been investigated theoretically at the...     

An Efficient One‐pot Access to Substituted Dihydropyrrol‐2‐one Derivatives Using Sucrose as Natural,Biodegradable and Inexpensive Catalyst

An efficient and simple procedure for the synthesis of highly substituted dihydropyrrol‐2‐ones has been developed via one‐pot four‐component condensation of amines, dialkyl acetylenedicarboxyaltes and formaldehyde in the presence of sucrose as an organocatalyst. The salient advantages of this method are using a natural, biodegradable and commercial available catalyst, good yields, short reaction times, simple work‐up and lack of need for column chromatography.