Oxidative addition of some geminal halonitroalkanes to iridium(I) and platinum(0) compounds

Oxidative addition of 1-chloro-1-nitroethane to trans-IrCl(CO)-[P(CH₃)₂C₆H₅]₂ followed by treatment of the initial product with pyridine yields a new iridium(III) complex IrCl(py)[COC(NO₂)CH₃][P(CH₃)₂C₆H₅]₂, whose structure has been confirmed by X-rays crystallography. Two intermediate products have been observed by NMR spectroscopy; their structures have been tentatively assigned. The reaction of the corresponding bromine derivatives yields two isomers of the composition IrBr₂(CO)[CH(NO₂)CH₃][P(CH₃)₂C₆H₅]₂, and these are not affected by pyridine. The reaction of 1-chloro-1-nitroethane with Pt[P(C₆H₅)₃]₄ takes a completely different course in that yields nitrorethane and cis-PtCl₂[P(C₆H₅)₃]₂ as the main products, with no detectable formation of the products of oxidation addition. A brief mechanistic investigation points towards the participation of radicals and radical anions as transient intermediates and a mechanism is proposed which explains most of the experimental results.     

Fluorine absorption spectra and some fluorides in condensed state

The absorption spectra of liquid F₂, NF₃, N₂F₄, CF₄, BF₃, NF₃, SF₆ have been obtained at diminished temperatures in the near ultra-violet region of the spectrum. It is shown that the absorption spectrum does not differ from the spectra in the gaseous phase, therefore the elementary absorption act is characterized by the cross section of photon absorption by an individual molecule. The absorption cross sections of the above mentioned molecules are represented in the liquid phase, which do not differ strongly from absorption cross sections of these molecules in the gaseous phase. The dependence of the absorption cross sections of liquid fluorine on its concentrations in solutions with N₂, Ar, NF₃, O₂ at - 196°C has been studied. The cross sections of photon absorption by the fluoride molecule in different liquid media with small fluorine concentrations have been obtained.     

Separation of molybdenum from tungsten with di(2-ethylhexyl)-phosphoric acid ac extractant

The use of di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant for the separation of molybdenum from tungsten was examined with the help of molybdenum-99 and tungsten-187 as radiotracers. Effective separation was obtained when the aqueous phase contained phosphoric acid at pH 0.8–2 or pH 3–3.5, depending on the amounts of metal. The method is applicable to both tracer and milligram amounts of molybdenum. The structure of the extracted species was examined by infrared spectroscopy.     

Structural studies on layered alkylpyridinium iodopalladate networks

The reaction of alkylpyridinium (CnH2n + 1NC5H5, hereafter Cn-Py) iodide salts in aqueous acetonitrile with a preformed palladium iodide precursor afforded two different types of organic-inorganic phases depending on the molar ratio. A 2:1 ratio yielded the phase [Cn-Py]2[PdI4] (3, n = 14, 16), which crystallized in the triclinic crystal system. The X-ray crystal structure of 3, (n = 14), refined in the space group P1 (a = 8.918(3) A, b = 9.894(3) A, c = 29.062(12) A, alpha = 93.51(3) degrees, beta = 94.17(3) degrees, gamma = 115.60(3) degrees, and Z = 2), consists of interdigitated bilayers with a basal spacing of 29.0 A. The aliphatic chains of the cations, which run almost parallel to the stacking direction, are fully stretched between polar planes built on isolated [PdI4]2- anions and cation headgroups. Changing the organic cation to palladium ratio to 1:1 led to a new phase [Cn-Py]2[Pd2I6] (4, n = 14, 16), which crystallizes in the triclinic P1 space group (a = 9.399(4) A, b = 14.264(6) A, c = 29.415(13) A, alpha = 92.11(4) degrees, beta = 90.07(4) degrees, gamma = 104.53(3) degrees, Z = 3 for 4(n = 14); a = 9.417(2) A, b = 14.215(3) A, c = 31.552(6) A, alpha = 87.96(3) degrees, beta = 87.63(3) degrees, gamma = 75.67(3) degrees, Z = 3 for 4(n = 16)). The layered structure is basically of a continuously interdigitated single-layer type, with a bilayer sublattice superimposed. Isolated [Pd2I6]2- anions contribute to the inorganic planes. A high degree of interdigitation and tilting of the aliphatic chains lead to basal spacings of 29.4 and 31.5 A for 4(n = 14) and 4(n = 16), respectively. The [Cn-Py]2[PdI4] and [Cn-Py]2[Pd2I6] phases were characterized by thermal analysis. Mesomorphic behavior was observed only for 3(n = 16), which was confirmed by variable-temperature powder XRD and optical microscopy.     

Synthetic and modified isoflavonoids XVII. Interaction of synthetic analogs of isoflavones with guanidine

Under the influence of guanidine, 1,3-benzodioxolane, 1,4-benzodioxane, and 1,5-benzodioxepane analogs of isoflavone are converted into 2-aminopyrimidine derivativesTranslated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 636–640, September–October, 1994.     

Cubic phases as structures of disclinations

We look for possible ordered geometrical configurations with bicontinuous or cellular topologies, optimizing the frustration of a periodic system of frustrated fluid films. The solutions found have the same symmetries as those observed for cubic phases of amphiphilic molecules. This agreement leads to consider cubic structures as structures of defects of rotation, or disclinations.This paper was presented at the workshop Ringing gels and Cubic phases, University of Bayreuth, October 25–26th, 1988.     

The synthesis of cis- and trans-1,2-dibromocyclopropane

A preparative route to cis- and trans-1,2-dibromocyclopropane ($\text{1}$) was developed via the Hunsdiecker reaction of silver cyclopropane-1,2-dicarboxylate ($\text{2}$). Cis- and trans-$\text{2}$ gave the same ratio of cis- and trans-$\text{1}$ (1:3.2). The mechanism of this reaction is briefly discussed.     

Nitration of 5-formyl-substituted 2-cyclopropylfurans and 2-methylfurans and the corresponding thiophenes

In the nitration of 5-formyl-substituted 2-cyclopropylfurans and the corresponding thiophenes, in addition to the formation of the corresponding 3-nitro derivative the replacement of the formyl group by a nitro group takes place. For a thiophene derivative the latter direction of the reaction is observed to a substantially smaller degree. Under nitration conditions, 5-formylsylvane is converted only into 5-nitrosylvane, while the corresponding formylmethylthiophene is nitrated exclusively in position 3. The difference observed in the behavior on nitration of the furans and thiophenes studied is explained by the different degrees of participation of the heteroatom in the delocalization of the charges in the heterocyclic ipso-ions formed as intermediates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 455–460, April, 1980.     

Proper determination of order of reactions by thermal analysis

The relationship 1– _m=1.062n ^1/1–n , well-known in non-isothermal kinetics and applied for determination of the kinetic exponentn, is not universal. A more accurate modification of the given equation is proposed in the form of a more complex function 1– _m=(n, X_m), whereX _m =E/RT _m is the dimensionless Arrhenius' criterion.     

Comportement thermique des propionates hydrates de calcium,strontium et baryum

Résumé Les propionates monohydratés de calcium, strontium et baryum ont été étudiés par radiocristallographie (sur monocristal et sur poudre) et par TG et ATD (à l'air et en milieu inerte). Ils cristallisent dans les systèmes monoclinique (Ca) ou orthorhombique (Sr, Ba). Ils perdent leur eau en une fois (Ca, Sr) ou deux fois (Ba) avec formation d'un hémihydrate intermédiaire. Tous les sels anhydres, d'abord amorphes aux rayons X, cristallisent vers 200°. Le propionate de baryum anhydre cristallisé subit une transformation polymorphique à 240°. Après 300° à l'air et 350° sous atmosphère inerte, la fusion et la décomposition se produisent simultanément: il y a dégagement de diéthylcétone et le résidu solide est du carbonate métallique bien cristallisé.

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The monohydrates of calcium, strontium and barium propionates have been investigated by radiocrystallography (using monocrystals and the powder method) and by TG and DTA (in air and in an inert atmosphere). These compounds crystallize in the monoclinic system (Ca) or the orthorhombic system (Sr, Ba). Dehydration occurs in a single stage for calcium and strontium propionates and in two stages for barium propionate. The compound Ba(C₂H₅CO₂) 0.5 H₂O is well-defined. All the anhydrous salts, first amorphous to X-rays, crystallize at about 200°. Barium propionate undergoes another phase transition at 240°. Melting and simultaneous decomposition take place after 300° in air and after 350° in an inert atmosphere, leading to evolution of diethylketone and to a solid residue of well-crystallized metal carbonate.

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Zusammenfassung Die Propionatmonohydrate von Calcium, Strontium und Barium wurden mittels Radiokristallographie (an Einkristallen und an Pulver), sowie mittels TG und DTA (in Luft und in inertem Medium) untersucht. Sie kristallisieren in monoklinen (Ca) oder orthorhombischen (Sr, Ba) Systemen. Sie verlieren ihr Kristallwasser auf einmal (Ca, Sr) oder zweimal (Ba) unter Bildung eines intermediären Hemihydrats. Sämtliche Anhydrosalze, welche sich zuerst bei Röntgenbestrahlung amorph verhalten, kristallisieren in der Nähe von 200°. Das kristalline wasserfreie Bariumpropionat erfährt eine polymorphe Änderung bei 240°. Nach 300° in Luft und 350° in inerter Atmosphäre treten Schmelzen und Zersetzung gleichzeitig auf: Diäthylaceton wird freigesetzt und der feste Rückstand besteht aus kristallinem Metallcarbonat.

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, , , . - () — Sr, Ba. , — . (₂₅)₂. 0,5₂. 200°. 240° . 300° 350° , .