Adducts of mononuclear oxomolybdenum(IV)O,O′-dialkyl(alkylene) dithiophosphate complexes with pyridine, 2,2′-bipyridyl and 1, 10-phenanthroline

Summary Equimolar adducts of mononuclear oxomolybdenum(IV)O,O-dialkyl and alkylene dithiophosphates with heterocyclic amines, MoO[S₂P(OR)₂]₂·L (where when R=Et,i-Bu; L=pyridine and when R=Et,n-Pr,i-Bu; L=2,2-bipyridyl, 1,10-phenanthroline) and (where G=CH₂CMe₂CH₂, L=2,2-bipyridyl and when G=CMe₂CMe₂; L=pyridine) have been prepared by reacting the corresponding oxomolybdenum(IV) complexes with an excess of pyridine or with bipyridyl or phenanthroline in a 11 molar ratio.The complexes have been characterized by elemental analyses and molecular weight determinations. Their probable structures are proposed on the basis of i.r. and n.m.r. (¹H,¹³C and³¹P) spectral data, which are consistent with a 6-coordinated octahedral structure for all the base adduct complexes.     

Schiff base complexes of dioxouranium(VI), III. Commun.: Dioxouranium(VI) complexes of bibasic tetradentateSchiff bases

Bibasic tetradentateSchiff bases having the donor system OH–NX–NX–OH have been shown to form UO₂(NO₃)₂(SBH₂) type of derivatives [SBH₂ is the molecule of the bibasic tetradentateSchiff bases such as HOC₆H₄C(R) N(CH₂) _n NC(R)C₆H₄OH (where R=H or CH₃ andn=2 or 3) and HOC(R)CHC(CH₃)N(CH₂) _n NC(CH₃)CH C(R)OH (where R=CH₃ or C₆H₅ andn=2 or 3)]. The 11 stoichiometry of these complexes is shown by elemental analysis and conductometric titrations. The molar conductence values in nitrobenzene indicate the non-electrolytic behaviour and the magnetic susceptibility measurements by the Gouy method show these complexes to be diamagnetic.With 1 Figure     

Unusual Reaction of 1,1,1-Trimethyl(allyldifluoro)disiloxane with Hexamethyldisiloxane

The reaction of 1,1,1-trimethyl(allyldifluoro)disiloxane with hexamethyldisiloxane gives rise to previously unknown ,-bis(trimethylsiloxy)oligoallylfluorosiloxanes Me₃SiO(FRSiO) _n SiMe₃ (n = 1-3) and -(trimethylsiloxy)--allyldifluorosiloxyoligoallylfluorosiloxanes Me₃SiO(FRSiO) _m SiRF₂ (m = 1 and 2), where R = CH₂ = CHCH₂.     

Synthesis of o-carboranesiloxanes and study of their reactivity

The coupling of dilithio-o-carborane with , -dichlorooligodimethylsiloxanes of type ClSi(CH₃)₂O[Si(CH₃)₂O]_nSi(CH₃)₂Cl with n from 1 to 3 has been performed. At a molar ratio of the reagent of 11, the products of the reaction are a five-membered ring compound, 1, 3-o-carboranetetramethyldisiloxane and a cyclodimethylsiloxane, and at a ratio of the reagents of 12, a seven-membered ring compound, 1, 5-o-carboranehexamethyltrisiloxane, and a cyclodimethylsiloxane. Attempts to open the seven-membered o-carboranesiloxane ring thermally or with the aid of acidic catalysts were unsuccessful. Under the influence of nucleophilic reagents, cleavage of the C-Si bond takes place with the splitting away of a silicon atom from the o-carborane nucleus and the formation of an o-carbonate and a cyclodimethylsiloxane.     

Radical addition of alkylbenzenes to α,α-dichlorovinyl compounds

Conclusions Toluene and p-xylene react with ,-dichloroolefins CCl₂=CHCH₂R (R = Cl, OCH₃, CH₂CH₃, and CH₂-CH₂ Cl) with tert-butyl peroxide initiation, to form adducts predominantly with the structure HCCl₂CH(CH₂C₆H₄X)-CH₂ R (X =p–CH₃), which corresponds to the orientation of the addition of the benzyl radicals to the -carbon atom of the chloroolefin with the formation of the more stable radicals. The formation of compounds CCl₂ = CHCH(CH₂C₆H₅)CH₂CH₂Y (Y = H and Cl) was also noted.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1809–1812, August, 1976.     

Phase equilibria and oxidation mechanisms in the LA-S-O system

The phase diagram of the La-S-O system at 1073 K was established with the vacuum seal technique. Six phases exist at this temperature: La₂O₃ (B-type), LaS₂, La₂S₃, La₂O₂SO₄, La₂O₂S and La₂O₂S₂. The thermodynamic functions for the reaction La₂O₂SO₄=La₂O₃+SO₂+1/2 O₂ were determined by using the emf method at temperatures from 1123 to 1373 K. The mechanisms of the oxidation reactions in the La-S-O system under different partial pressures of oxygen (–4.4 < log <–0.7) were also investigated by means of DTA, TG and powder X-ray diffractometry.

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Zusammenfassung Das Phasendiagramm des La-S-O-Systems bei 1073 K wurde bestimmt. Bei dieser Temperatur liegen 6 Phasen vor, und zwar La₂O₃ (B-Typ), LaS₂, La₂S₃, La₂O₂SO₄, La₂O₂S und La₂O₂S₂. Für die Reaktion La₂O₂SO₄=La₂O₃+SO₂+1/2 O₂ wurden die thermodynamischen Funktionen im Temperaturbereich von 1123–1373 K nach der EMF-Methode bestimmt. DTA, TG und Pulver-Röntgendiffraktometrie wurden zur Untersuchung der Mechanismen der im La-S-O-System verlaufenden Oxydationsreaktionen herangezogen, wobei der Sauerstoffpartialdruck in den Grenzen von – 4.4 < log < <-0.7 variiert wurde.

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La-S-O 1073 . : La₂O₃ (-), LaS₂, La₂S₃, La₂O₂SO₄, La₂O₂S La₂O₂S₂. . . ., La₂O₂SO₄=La₂O₃+ SO₂+1/2 ₂ 1123–1373. , La-S-O –4.4 < log < –0.7.

     

Oxidative splitting of secondary cycloalkanols by Pb(OAc)4-LiCl AND Pb(OAc)4-Cu(OAc)2 systems

Conclusions As the result of the reaction of cyclopentanol and cyclohexanol with the Pb(OAc)₄-LiCl and Pb(OAc)₄-Cu(OAc)₂ systems, -formylalkyl radicals CH₂(CH₂)_n+1CHO (n=2, 3) are formed, which are oxidized by these systems into -chloroalkanals and -alkenals, respectively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1345–1348, June, 1984.     

WDS-EPMA nitrogen profile determination in TiN/Ti diffusion couples using homotypic standard materials

Wavelength-dispersive electron probe microanalysis (WDS-EPMA) of TiN/Ti diffusion couples was carried out in order to determine the nitrogen profiles across the phase bands. Thein situ TiN/Ti diffusion couples were used for phase equilibrium studies. The problem of complete overlap of the Ti _L1 and N _K lines was solved using chemically well-characterized single-phase titanium nitride samples (-Ti(N), -Ti₂N and -TiN_1–X ) as external standards. By using such homotypic standard materials it was possible to eliminate systematic errors introduced by imperfect correction algorithms. The composition of the phases in multiphase TiN/Ti diffusion couples could be determined with an accuracy of better than ±1 at% N.     

Acyl Iodides in Organic Synthesis: I. Reactions with Alcohols

Reaction of acyl iodides RC(O)I (R = Me, Ph) with alcohols R'OH (R' = Me, Et, i-Pr, t-Bu, CH₂ = CHCH₂, HCCCH₂) provides in the corresponding organyl iodides R'I. Unlike that 2-chloroethanol and phenol (R' = CH₂CH₂Cl, Ph) react with RC(O)I in the same way as with acyl chlorides yielding esters RCO₂R'. This reaction path occurs partially also with methanol and ethanol.     

Reactivity of oxalates of La(III), Ba(II) and Cu(II) in ternary mixtures

Composites of cuprates of La(III) and Ba(II) were obtained by decomposing mixtures of oxalates of La(III), Ba(II) and Cu(II) prepared in 111 and 123 mol proportions respectively and sintering the oxide products at 1173 K. Reactions studied by TG, DTA and XRD techniques revealed the following features: (i) Decomposition of oxalates of La(III) and Ba(II) is drastically affected in mixtures. Decomposition temperature of organic part in the former (111) is shifted by 100 K while that of BaCO₃ in the case of latter (123) is shifted by 400 K towards lower temperature side. (ii) All exothermic peaks on DTA traces of both the mixtures are allotted to the decomposition of oxalates to Cu₂O, La₂O₂CO₃ and BaCO₃ phases while endothermic peaks around 863 and 1083 K are assigned for BaCuO₂ and La₂CuO₄ phases respectively in the case of former (111) and endothermic peaks at about 1068, 1136 and 1213 K are correlated with BaCuO₂, a composite of La₂O₃, La₂CuO₄ and La_0.5Ba_0.5CuO_3– (0.5) phases and LaBa₂Cu₃O_7– (0) phase respectively in the case of latter (123) and (iii) Lines of all cuprate compounds appear in XRD patterns of those samples preheated at temperatures 873 K. The following reaction is proposed in the case of 123 mixture: Authors are deeply thankful to the Authorities of Department of Atomic Energy (DAE), Goverment of India, for providing the funds for research project and to Professor A. V. Phadke, Department of Geology, University of Poona, for the valuable discussion.     

ESR spectroscopic investigation of steric and polar factors in the addition of radicals to unsaturated compounds

The rate constants of the addition of CCl₃CH₂ClCH₃(R⁶) radicals to -methyl-styrene, styrene, methyl methacrylate, methyl acrylate, and acrylonitrile and of CCl₃CH₂(CH₃)₂(R⁷) radicals to styrene, methyl acrylate, and acrylonitrile were determined by ESR spectroscopy. It was shown that the radicals R⁶ and R⁷ possess approximately equal reactivity in addition to unsaturated compounds, despite the difference in the donor-acceptor properties of the substituents at the vinyl group. In a comparison of the reactivity of radicals R⁶ and R⁷ with the reactivity of radicals CCl₃CH₂H₂(R¹), CCl₃CH₂HCH₃(R³), CCl₃CH₂HCl(R⁴), and ClCH₂CH₂Cl₂(R⁵) [1] in addition reactions, it was shown that polar and steric effects of the substituents situated in the -position to the radical site of the above-mentioned radicals, as well as the donor-acceptor properties of the substituents at the vinyl group in the unsaturated compounds, lead to appreciable changes in reactivity.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 136–141, January, 1992.     

Metal phenyl compounds as cotatalysts in the homogeneous metathesis of alkenes

The application of several metal phenyl compounds as active cocatalysts in the homogeneous metathesis of alkenes with WCl or MoCl is described. Promising results have been obtained by using Sn(C₆H₅)₄, Sn(C₆H₅)₃Cl, Pb(C₆H₅)₄ and Pb(C₆H₅)₃Cl.

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- , WCl₆ MoCl₅. qH Sn(C₆H₅)₄, Sn(C₆H₅)₃Cl, Pb(C₆H₅)₄ Pb(C₆H₅)₃Cl.

     

Reactions of the radical cations of aliphatic aldehydes in freon matrices

ESR spectra of -irradiated, at –196 °C, solutions of acetic and propionic aldehydes in freon-11 and freon-113 affected by aldehyde concentration, temperature, and the action of light have been studied. It has been shown that the radical cations CH₃CHO⁺ are converted into neutral radicals CH₃O and CH₃HOH and the cations CH₃CH₂CHO⁺. are converted to RO and CH₃HCHO due to ion-molecular reactions of proton transfer /CH₃O and CH₃HCHO/ of hydrogen atom transfer /CH₃HOH/.     

MO-Berechnungen an Heterocyclen, 1. Mitt.: Die Anwendung verschiedener SCα-Techniken auf pyrrol-und pyridinartige Heterocyclen

Zusammenfassung Die Untersuchungen beschäftigen sich mit der Anwendbarkeit verschiedener SC-LCAO-MO-Verfahren inHückelscher Näherung (SC-HMO) auf Heterocyclen.Die vorliegende Arbeit untersucht den Einfluß der Iterationsbeziehungen zwischen _r undq _r nach der - und -Technik an pyrrol-und pyridinartigen Verbindungen. Durch Variation von als auch des Korrekturparametersh _y für das Coulombintegral _y des Heteroatoms y läßt sich der Einfluß dieser Größen auf verschiedene MO-Daten bestimmen. Die Bedeutung der beiden SC-Verfahren für einige MO-Daten wird diskutiert.

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Our work deals with the applicability of different SC LCAO MO methods in theHückel approximation (SC HMO) on heterocycles.This paper examines the influence of the iteration relations between _r andq _r with the -and -technique on pyrrole- and pyridine-like compounds. By variation of andh _y — the correction parameter for theCoulomb integral _y of the heteroatom y — the influence of these magnitudes on MO quantities can be determined. The importance of the two SC-methods for some MO quantities is discussed.

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Mit 2 Abbildungen     

Dechlorination of pentachloro derivatives of the type CHCl2CCl2CH2CHClR

Conclusions Reaction of polychloro derivatives of formula CHCl₂CCl₂CH₂CHClR (R =H, CH₃, Cl, or CH₂OH) with zinc in ethanol results in dechlorination with the formation of high yields of mixtures of relatively easily separated E and Z isomers of the corresponding ,-dichlorovinyl derivatives.Translated from Izvestiya Akademii Nauk SSSR Seriya Khimicheskaya, No. 3, pp. 686–688, March, 1976.     

New polyhydroxysteroids from the far-eastern starfish Henricia sp.

From the far-eastern starfishHenricia sp. we have isolated and characterized the new polyhydroxysteroid (24S)-5-cholestane-3,4,6,8,15,24-hexaol and three new glycosides: (24S)-5-cholestane-3,4,6,8,15,24-hexaol 3-O-(2,4-di-O-methyl--D-xylopyranoside) (henricioside H₁), 24-methyl-5-cholesta-4,22E-diene-3,6,8,15,16,26-hexaol 3-O-(2,3-di-O-methyl--D-xylopyranoside) (henricioside H₂), and the 22,23-dihydro derivative of henricioside H₂ (henricioside H₃).Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 249–253, March–April, 1993.     

Diastereoselective addition of organomanganese compounds to chiral polyalkoxyaldehydes

Organomanganese compounds RMnI (R=Me, Pr, Bu, Hex, Ph, BuCC) prepared from RLi and MnI₂ in Et₂O react with 3-O-benzyl-1,2-O-isopropylidene--D-xylo-pentodialdo-1, 4-furanose, 1,23,4-di-O-isopropylidene--D-galacto-hexodialdo-1,5-pyranose, andR-2,3-dibenzyloxypropanal to afford 4,5-threo-, 5,6-threo-, and 2,3-threo-isomeric products, respectively, with high diastereoselectivity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1122–1126, June, 1993.     

Calorimetric study of oxygen bond strength in the surface layer of manganese dioxide

The heat of oxygen removal from the MnO₂ surface (q_s) during its reduction by carbon monoxide and the heat of reoxidation of the reduced surface by gaseous oxygen (q_s) have been determined by a calorimetric method at 100 and 200°C. At 200°C both q_s and q_s are close to the enthalpy of MnO₂ transformation to Mn₂O₃. At 100°C the reduction of MnO₂ takes place without any distinct formation of a phase of the lower oxide, however, it leads to significant changes in both the surface and the subsurface layer of the oxide.

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100° 200°C MnO₂ (q_s) (q_s). 200°C q_s, q_s ( ) MnO₂ Mn₂O₃. 100°C MnO₂ , .

     

Tribracchial lariat ethers: Syntheses,binding, and formation of an intramolecular macroring-sidearm complex in the absence of any cation

Details of a new synthetic approach to 4,10,16-triaza-18-crown-6 (triaza-18-crown-6) are reported, along with the preparation and binding properties of the following derivatives having the indicated sidearms: CH₂CCH, CH₂CH₂OH, CH₂CH₂OCH₃, COCH₂OCH₃,CH₂COOCH₂CH₃, CH₂C₆H₅, and CH₂C₆H₄–2–NO₂. A key intermediate in the synthesis of triaza-18-crown-6 is 4-N-toluenesulfonyl-1,7,13-trioxa-4,10,16-triazacyclooctadecane-9,17-dione. This compound is found by solid state structure analysis to fold to form an intramolecular, doubly-hydrogen bonded complex in which the two N-H protons interact with the two tosyl group oxygens. Details of the structure are reported.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Gas phase electrocatalytic reduction of carbon monoxide in a cell with a solid proton-conducting electrolyte

Gas phase reduction of carbon monoxide to methanol and ethanol was found to occur in electrochemical cells with solid proton-conducting electrolytes based on H₃PW₁₂O₄₀· nH₂O, H₄SiW₁₂O₄₀ · nH₂O or Sb₂O₅ · 3.5 H₂O and metallic Ni, Pd or Cu electrodes at room temperature under atmospheric pressure.

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, H₃PW₁₂O₄₀·nH₂O, H₄SiW₁₂O₄₀·n H₂O Sb₂O₅·3,5H₂O Ni, Pd Cu CO .