Structure Development in Simple Cross-Linked Organopolysiloxanes

13C CP and CPPI MAS NMR have been carried out on thermally cured samples of polymethylvinylsiloxane and polydimethylsiloxane. By varying the CP contact time, the and vinyl carbons and the methyl carbon of the CH3–(SiO<)–CH=CH2 species could be identified. A further methyl carbon was detected which was less mobile and which we assign to methyl groups attached to silicon species on which the vinyl group has reacted to form a cross-link. Resonance from – CH2– carbons was observed in the 30–40 ppm range, and these species arise from methyl-vinyl cross-linking to give CH3–(SiO<)– H2– H2–(SiO<)–CH=CH2. Higher temperature curing promotes vinyl-vinyl cross-linking to give CH3–(SiO<)–CH2– H–CH2–(SiO<)–CH3 links between chains. Evidence for this comes from the insensitivity of the carbon resonance under CPPI, indicating that it is in a – CH= rather than a =CH2 environment. There was also evidence of –CH2– carbons in the polydimethylsiloxane material, suggesting that thermally activated, methyl-methyl cross-linking can occur to give CH3–(SiO<)– H2– H2(SiO<)–CH3 links between chains.     

Structural Investigation of the First Stages of Pyrolysis of Si-C-O Preceramic Polymers Containing Si–H Bonds

The polymer-to-glass transformation in the Si-C-O system usually involves cross-linking reactions at the C sites, which transform for example Si– H3 sites into (Si)4 sites, leading to the formation of a silicon oxycarbide network. Identification of the various C sites that form during pyrolysis under inert atmosphere is rather difficult from 13C MAS-NMR spectra, due to strong overlap of resonance lines, which prevents an accurate determination of the chemical shift values. This paper reports on the use of a spectral editing technique called Inversion Recovery Cross Polarization (IRCP), which, when combined with Cross Polarization (CP) technique, allows us to identify and quantify the formation of Si- H2-Si bridges during the early stages of the pyrolytic transformation of a polysiloxane containing Si–CH3 and Si–H groups. Several Si-C-O systems characterized by the same initial number of Si–CH3 bonds but with increasing number of Si–H bonds, have been investigated by MAS-NMR as well as thermogravimetric analysis coupled with mass spectrometry (TG/MS). The Si—H bonds play clearly an active role in the insertion of C atoms within the silica network.     

Preparation,Structure, and Reactivity of ≡Si– $${\text{N}}^ \cdot$$ –H Radicals

A method is developed for the synthesis of Si– –H radicals on a silica surface and information is obtained by ESR and quantum chemical calculations of model systems on their structure and spectral (radiospectroscopic) characteristics. The reactivity of these radicals toward CO, H₂, and H₂=H₂ molecules is studied. The structure of the Si–HN– =O radical is analyzed, which is the product of CO addition. The kinetic and thermochemical characteristics of processes with the participation of synthesized radicals are determined.     

Synthesis and magnetic properties of trinuclear nickel(II) complexes bridged by α-benzyldioximato groups

Four new NiII–NiII–NiII homotrinuclear complexes namely [Ni(-BD)2{NiL2}](ClO4)2 [L = 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (5-NO2-phen), 2,2-bipyridyl (bpy) or 4,4-dimethyl-2,2bipyridyl (Me2bpy) and (-BD)– = -benzyldioximato ion] have been prepared and characterized. Based on elemental analyses, i.r. spectra, conductivity measurements, extended -benzyldioximato-bridged systems consisting of three nickel(II) ions in which the central nickel(II) ion has a square-planar environment and the end capped two nickel(II) ions have a distorted octahedral environment are proposed for these structures. The temperature dependence of the magnetic susceptibility for complexes (1) (phen), (2) (5-NO2-phen), (3) (bpy) and (4) (Me2bpy) were measured over the 77–300 K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator (H^ = –2JS^1S^2), giving the exchange integral J = –13.31 cm–1 for (1), J = –7.37 cm–1 for (2), J = –8.96 cm–1 for (3) and J = –7.33 cm–1 for (4) These results indicate a weak antiferromagnetic spin exchange interaction between the two terminal nickel(II) io     

O-H ... O(S) hydrogen bonds in 2-hydroxy(thio)benzamides. Survey of spectroscopic and structural data

Summary From a survey of spectroscopic and structural data of six corresponding 2-hydroxybenzamides and 2-hydroxythiobenzamides (amide, N-methylamide, N,N-dimethylamide, piperidide, morpholide, 2,6-dimethylpiperidide) remarkable similarities between O(N)-H ... O and O(N)-H ... S hydrogen-bonds are obtained, concerning both, hydrogen-bond patterns and hydrogen-bond strengths. In dilute solution the OH groups of all compounds are intramolecularly associated to the (thio)carbonyl O (S) atoms with distinctly larger hydrogen-bond strengths for primary and secondary amides [ (O-H)=2950–3020 cm^–1, (OH)=12.16–11.99 ppm] and thioamides [ (O-H)=2960–3000 cm^–1, (OH)=11.65–11.13 ppm], than for tertiary amides [ (O-H)=3200–3250 cm^–1, (OH)=9.95–8.95 ppm] and thioamides [ (O-H)=3245–3330 cm^–1, (OH)=8.09–7.06 ppm]. In the solid state, the OH groups of the primary and secondary (thio)amides are also engaged in rather strong intramolecular O-H ... O=C [O ... O=2.51 Å, (O-H)=2700–2750 cm^–1] and O-H ... S=C [O ... S=2.90–2.94 Å, (O-H)=2700–2840 cm^–1] hydrogen-bonds; thetrans-NH groups of the primary (thio)amides and the NH groups of the secondary (thio)amides connect the molecules to N-H ... O-H [N ... O=2.93–3.10 Å, (N-H)=3319–3407 cm^–1] hydrogen-bonded chains; the remainingcis-NH groups of the primary (thio)amides give rise to eight-membered cyclic dimers via N-H ... O=C [N ... O=2.93 Å, (N-H)=3226 cm^–1] and N-H ... S=C [N ... S=3.46–3.47 Å, (N-H)=3233–3277 cm^–1] hydrogen-bonds. Contrary, the OH groups of the tertiary (thio)amides are intermolecular associated in the solid state and link the molecules to O-H ... O=C [O ... O=2.63–2.75 Å, (O-H)=3075–3135 cm^–1] and O-H ... S=C [O ... S=3.18–3.26 Å, (O-H)=3130–3190 cm^–1] hydrogen-bonded chains.

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O-H ... O(S)-Wasserstoffbrückenbindungen in 2-Hydroxy(thio)benzamiden. Ein Überblick über spektroskopische und strukturelle Daten

Zusammenfassung Aus einer Zusammenstellung von spektroskopischen und strukturellen Daten von sechs entsprechenden 2-Hydroxybenzamiden und 2-Hydroxythiobenzamiden (Amid, N-Methylamid, N,N-Dimethylamid, Piperidid, Morpholid, 2,6-Dimethylpiperidid) ergeben sich bemerkenswerte Analogien zwischen O(N)-H ... O und O(N)-H ... S H-Brücken, die sowohl die H-Brücken-Muster als auch die H-Brücken-Stärken betreffen. In verdünnter Lösung sind die OH-Gruppen aller Verbindungen intramolekular mit den O(S)-Atomen der (Thio)Carbonylgruppen assoziiert, wobei die H-Brücken bei den primären und sekundären Amiden [ (O-H)=2950–3020 cm^–1, (OH)=12.16–11.99 ppm] und Thioamiden [ (O-H)=2960–3060 cm^–1, (OH)=11.65–11.13 ppm] deutlich stärker sind, als bei den tertiären Amiden [ (O-H)=3200–3250 cm^–1, (OH)=9.95–8.95 ppm] und Thioamiden [ (O-H)=3245–3330 cm^–1, (OH)=8.09–7.06 ppm]. Im Festkörper weisen die primären und sekundären (Thio)Amide ebenfalls sehr starke intramolekulare O-H ... O=C [O ... O=2.51 Å, (O-H)=2700–2750 cm^–1] und O-H ... S=C [O ... S=2.90–2.94 Å, (O-H)=2700–2840 cm^–1] H-Brücken auf; dietrans-NH-Gruppen der primären (Thio)Amide und die NH-Gruppen der sekundären (Thio)Amide verknüpfen die Moleküle über N-H ... O-H H-Brücken [N ... O=2.93–3.10 Å, (N-H)=3318–3407 cm^–1] zu Ketten; die verbleibendencis-NH-Gruppen der primären (Thio)Amide bilden zyklische, über N-H ... O=C [N ... O=2.93 Å, (N-H)=3226 cm^–1] und N-H ... S=C [N ... S=3.46–3.47 Å, (N-H)=3233–3277 cm^–1] H-Brücken gebundene, 8-Ring-Dimere. Im Gegensatz dazu sind die OH-Gruppen der tertiären (Thio)Amide im Festkörper intermolekular assoziiert und verknüpfen die Moleküle über O-H ... O=C [O ... O=2.63–2.75 Å, (O-H)=3075–3135 cm^–1] und O-H ... S=C [O ... S=3.18–3.26 Å, (O-H)=3130–3190 cm^–1] H-Brücken zu Ketten.

     

Untersuchung der Ionengleichgewichte in Tetrahydrofuranlösungen des 2-Naphthonitril-Natriums

With the aid of conductometric measurements the ion equilibria inTHF solutions of 2-naphthonitrile sodium were studied. It was established that in the concentration interval of 10^–4–10^–5 mol/l the equilibrium ion pairs—free ions is predominant . The ion pairs are contact (average interion distance about 4.1 Å). In the temperature interval of 25 to 40° the heat of dissociation –H=3.1 kcal/mol, whereas between –40 and –70°–H is 1.26 kcal/mol. At higher concentrations (10^–2–10^–3 mol/l) triple ion formation is observed.     

Controlling the viscosity of melts of partially crystalline polyimides used for preparing carbon-reinforced plastics

The influence exerted by the molecular weight of partially crystalline polyimide derived from 4,4-bis(4-aminophenoxy)diphenyl and 1,3-bis(3,4-dicarboxyphenoxy)benzene on the viscosity of its melt was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1370–1373.Original Russian Text Copyright © 2004 by Kostereva, Panov, Didenko, Silinskaya, Svetlichnyi, Yudin, Kudryavtsev.     

The mutual catalytic effect in kinetic reactions and its application to simultaneous determination of binary components

The mutual catalytic effect between iron(II) and antimony(III) on the chromium(VI)-iodide kinetic reactions has been studied by stopped-flow FIA. The concept of mutual catalytic coefficient is defined. The deviations from additive principles of absorbance within certain concentration ranges in previous procedures can be compensated effectively, by introducing the mutual catalytic coefficient into the simultaneous determination of a binary mixture with stopped-flow-FIA method. The linear concentration ranges have been enlarged, 0–3.5 g/ml Fe(II) and 0–3.7 g/ml Sb(III) compared with 0–1.2 g/ml Fe(II) and 0–2.0 g/ml Sb(III) without use of the coefficient. Iron and antimony contents in wastewater, a simulated sample and a zinc standard were determined, the recoveries and relative standard deviations being, respectively, 99.8–101.3% and 2.7–3.6% for iron and 95.4–100.3% and 2.3–5.3% for antimony compared with 95.2–98% and 3.0–4% for iron and 96–104% and 4.5–4.8% for antimony, assuming additivity.     

Synthesis and characterization of new poly[phenylquinoxaline(ether)imides]

A series of new aromatic poly[phenylquinoxaline(ether)imides] were synthesized by solution polycondensation of aromatic diamines containing preformed phenylquinoxaline groups with dianhydrides having ether linkages and isopropylidene or hexafluoroisopropylidene units. All polymers are readily soluble in polar organic solvents (N-methylpyrrolidinone, DMF, dimethylacetamide) and in less polar liquids such as chloroform. Very thin coatings were deposited onto silicon wafers. According to atomic force microscopy, they had a smooth, pinhole-free surface. The polymers showed high thermal stability with decomposition temperatures above 470 °C and glass transition temperatures in the range of 210–238 °C, being thus characterized by a large gap between the glass transition and decomposition temperatures.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th year anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1952–1957, September, 2004.     

Linear polynuclear tetrazole-containing compounds

Linear polynuclear tetrazole-containing compounds were synthesized. Alkylation of 5-[-(5-phenyl-2-tetrazolyl)alkyl]tetrazoles with ethyl bromoacetate and chloroacetamide gave the corresponding esters and amides. Treatment of the latter with tetrachlorosilane-sodium azide afforded compounds containing three tetrazole rings linked through polymethylene bridges. Acid ionization constants of the products possessing an NH-tetrazole ring (pK _a = 2.9–3.2) and the corresponding carboxylic acids (pK _a = 2.9–3.1) in aqueous methanol were determined by potentiometric titration.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1580–1586.Original Russian Text Copyright © 2004 by Morozova, Komissarov, Esikov, Zubarev, Malin, Ostrovskii.     

Thermochemistry of heteroatomic compounds

The enthalpies of combustion (H _comb) of 13 primary, secondary, and tertiary alkylphoshines in the condensed state were calculated using the equation H _comb = –860.7 – 107.0N, where N is the number of valent (bond-forming) electrons. This equation can be used for the calculation of enthalpies of combustion and formation of phosphoric acid esters.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1693–1694, August, 2004.     

Essential oil ofPerovskia angustifolia from Kyrgyzystan

The water distilled essential oils from leaves ofPerovskia angustifolia (Labiatae) collected from three different localities in the Arslonbob mountains of Kyrgyzystan were analyzed by GC/MS. 1,8-Cineole (12.0–27.5%), -pinene (7.3–14.7%), epi-13-manool (3.8–12.6%) bornyl acetate (1.2–8.7%), camphene (2.5–6.8%), camphor (4.3–6.5%), -caryophyllene (3.2–6.5%), caryophyllene oxide (1.7–5.9%), -humulene (2.1–5.2%), humulene epoxide II (1.9–4.8%), caryophylladienol (1.4–4.3%), and borneol (3.0–3.2%) were found as major constituents.Materials presented at the 2nd International Conference of Natural Compounds.Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 386–388, May–June, 1997.     

Adsorptive voltammetric procedure for the determination of platinum baseline levels in human body fluids

Summary An extremly sensitive procedure for the determination of platinum in human body fluids is presented. A high pressure decomposition of the samples is followed by adsorptive voltammetric measurement. A detection limit down to 0.2 ng Pt/l sample allowed baseline levels of platinum in body fluids (urine: 0.5–15 ng/l, blood and blood plasma: 0.8–6.9 ng/l) to be evaluated. The concentration ranges in body fluids of occupationally exposed people were determined to 21–2900 ng/l (urine), 32–180 ng/l (blood) and 95–280 ng/l (blood plasma).     

Solubilization compositions for template synthesis of mesoporous sorbents

The suitability of mixed solubilization compositions for template synthesis of mesoporous molecular sieves of various designations was demonstrated by analysis of published data and by the authors experimental results.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 11, 2004, pp. 1787–1794.Original Russian Text Copyright © 2004 by Yaroshenko, Ilin.     

Study of the catechins and proanthocyanidins ofQuercus robur

More than 20 compounds have been isolated from the bark ofQuercus robur. Monomers: (–)-epicatechin, (–)-epicatechin gallate, (+)-catechin, (+)-catechin gallate, (+)-gallocatechin, (–)-epigallocatechin, and (–)-epigallocatechin gallate; dimeric proanthocyanidins: (+)-catechin-(4-8)-(+)-catechin, 3-O-galloyl-(+)-catechin-(4-8)-3-O-galloyl-(+)-catechin, 3-O-galloyl-(+)-gallocatechin-(4-8)-(+)-gallocatechin, (–)-epicatechin-(4-8)-3-O-galloyl-(–)-epigallocatechin gallate, 3-O-galloyl-(–)-epicatechin-(4-8)-3-O-galloyl-(–)-epigallocatechin, 3-O-galloyl-(–)-epigallocatechin-(4-8)-(+)-catechin; and oligomeric proanthocyanidins: D14-D19.Materials presented at the IInd International Symposium on the Chemistry of Natural Compounds (SCNC, Eskiehir, Turkey, October, 22–24, 1996).Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 40 64 75. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 819–833, November–December, 1997.     

Structural flexibility of the (η<Superscript>3</Superscript>-allyl)· Palladium complex with sorbic acid

The density functional theory method was used to study the structural flexibility of a hydroxyl-containing (³-allyl)palladium complex with sorbic acid [(³-C₃H₃(CH(OH)CH₃)(COOH))PdCl₂]^– and its analog [(³-C₃H₃(CH(OH)CH₃)(COO))PdCl₂]^2–. Potential surfaces of internal rotation in the CH(OH)CH₃ substituent at the terminal carbon atom of the allyl fragment have been constructed for the complexes. It is found that weak hydrogen bonds COOH...Cl and OH...Cl are formed in the molecules. Various types of structural deformation of the complex are discussed.Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 435–441, May–June, 2004.Original Russian Text Copyright © 2004 by T. A. Morozova, A. P. Belov, and A. V. Krylov     

Tensimetric investigation of the CrCl<Subscript>3</Subscript>—Cl<Subscript>2</Subscript> system in the temperature range of 600–1200 K

The sublimation pressure of chromium trichloride was measured by the static method with a quartz membrane-gauge manometer in the temperature range of 875–1230 K. An approximating equation for the sublimation pressure vs. temperature was found. The enthalpy (259.4±4 kJ mol^–1) and the entropy (224.2±3.5 J mol^–1 K^–1) of sublimation at 298 K were calculated. For the process 2 CrCl₃(g) + Cl₂(g) = 2 CrCl₄(g), the following values were obtained: _r H°₂₉₈ = –207.1±11.6 kJ mol^–1 and _r S°₂₉₈ = –173.6±10 5 J mol^–1 K^–1.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1561–1564, August, 2004.     

Complexation of copper(II) with β-<Emphasis Type="Italic">tert</Emphasis>-butyl L-aspartate in the presence of anionic surfactant

Complexation of copper(II) with -tert-butyl L-aspartate in aqueous solutions of the anionic surfactant, sodium dodecyl sulfate, was studied by spectrophotometry, followed by mathematical processing of the results. Compositions of complexes and equilibrium constants of their formation reactions were determined.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 860–861.Original Russian Text Copyright © 2004 by Vladimirova, Vladimirov.     

Distribution of natural radionuclides

The distribution of natural nuclides and of the effective specific radioactivity in processing of the sphene concentrate was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1237–1240.Original Russian Text Copyright © 2004 by Melnik, Lokshin, Sedneva.