Infrared intensities of the external modes of crystalline nitrous oxide

The absorption intensities of two infrared active lattice modes of crystalline N₂O have been measured. Both the frequencies and intensities of the external modes of N₂O have been found to be very similar to those of CO₂, and most of the differences between the spectra of CO₂ and N₂O can be explained by the differences in the quadrupole moments.     

Synthesis and structural characterization of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2: An organometallic complex containing a chelating acetate ligand

The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH₃CO₂)Mn(CO)₂[P(C₆H₅)₃]₂, has been accomplished by the reaction of NaMn(CO)₅ with (CH₃)₃SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry $\text{P}\text{2}{}_1\text{c}$ and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C₆H₅)₃ bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C₆H₅)₃ bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor.     

Bestimmung der molaren Masse und der Ladungszahl von Polymerelektrolyten mit der Ultrazentrifuge

Zusammenfassung In der vorliegenden Arbeit wird das Sedimentationsgleichgewicht der Systeme Na₆[H₂W₁₂O₄₀]—NaCI—H₂O und Na₆[H₂W₁₂O₄₀]—NaClO₄— H2O untersucht. Die scheinbare molare Masse Mapp des Natriummetawolframats wird in beiden Systemen als Funktion der Natriummetawolfrarnat-Anfangspartialdichte ₀ ^PX _z gemessen. Durch lineare Extrapolation der Funktion Mapp = Mapp (PP,, ) auf die Polymerelektrolyt-Anfangspartialdichte Null können die Grenzwerte der scheinbaren molaren Masse (Mapp)o ermittelt werden. Aus den (Mapp)o-Werten wird die Abhängigkeit der Größe (ln _PXz /m _BX ) _mPXz von der NaCI- bzw. NaClO₄-Molalität berechnet.Die Bestimmung der molaren Masse und der (stöchiometrischen) Ladungszahl eines Polymerelektrolyten aus den experimentell ermittelten (Mapp)o-Werten unter Anwendung der Lamm-Williams-Gleichung wird diskutiert. Zur Ermittlung der beiden Größen müssen mehrere Versuchsreihen mit zwei verschiedenen Fremdelektrolyten durchgeführt werden. Externe Messungen sind nicht erforderlich.Man erhält auf diese Weise verläßliche Werte so-wohl der molaren Masse als auch der (stächiometrischen) Ladungszahl.

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Summary The sedimentation equilibria of the systems sodium metatungstate-sodium chloride-water and sodium metatungstate-sodium perchlorate-water are investiated. In both systems the apparent molecular mass Mapp of sodium metatungstate (PX _z) is measured in dependence on partial density ₀ ^PX _z before centrifugation. By linear extrapolation of the function Mapp = Mapp ( ₀ ^PX _z the limiting value (Mapp)o for ₀ ^PX _z = 0 is obtained. The variation with sodium chloride and sodium perchlorate molality of the quantity (ln _{PX z} ^m _BX )mPX_z is calculated from (Mapp)o data.The determination of the molecular mass and the algebraic valency of a polymeric ion by means of the (Mapp)o values calculated by Lamm-Williams equation is discussed. In order to obtain these two quantities at least two series of experiments are required, each of which using a different supporting electrolyte. External measurements are not necessary. In this way reliable values for the molecular mass as well as for the stoichiometric valency are obtained.

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Mit 5 Abbildungen und 3 Tabellen     

Telomerization of ethylene with 1,1,1,3-tetrachloropropane in the presence of iron pentacarbonyl and isopropyl alcohol

Conclusions Polychlorinated hydrocarbons containing the CCl₃ group can be used as telogens in the telomerization of olefins in the presence of iron pentacarbonyl and i-C₃H₇OH. The formation of the telomer homologs in high yield obeys the general rules that were established for the given initiating system.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2837–2839, December, 1971.     

Die Kristallstruktur des W3CoB3 und der dazu isotypen Phasen Mo3CoB3, Mo3NiB3 und W3NiB3

Zusammenfassung Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃ und W₃NiB₃ kristallisieren in einem eigenen Typ (W₃CoB₃-Struktur). Das trigonal prismatische Bauelement [T ₆B]^* ist zu Ketten vereinigt, wobei B₃-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.

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The crystal structure of W₃CoB₃ and the isotypic phases Mo₃CoB₃, Mo₃NiB₃, and W₃NiB₃

Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃, and W₃NiB₃ were found to possess a new type of crystal structure (W₃CoB₃-structure type). Trigonal prismatic groups [T ₆B]^* are linked together forming chains in such a way that B₃-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

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Mit 2 Abbildungen     

Purification of 3-ethoxycarbonylquinuclidine and its conversion to 3-quinuclidinecarboxylic acid and 3-quinuclidinylmethanol

3-Ethoxycarbonylquinuclidine obtained by the Grob method is a mixture of 3-ethoxycarbonyl-1-azabicylo-[2.2.2]- and, according to ¹³C NMR data, 5-ethoxycarbonyl-5-azatricyclo[3.2.1.0^2,7]octanes (1621). 3-Ethoxy-carbonylquinuclidine was purified by recrystallization of the hydrochloride, hydrolyzed by water to 3-quinuclidinecarboxylic acid, and reduced by LiAlH₄ to 3-quinuclidinylmethanol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, 1509–1512, November, 1992.     

Complex study of nickel skeleton catalysts: V. Study of novel non-pyrophoric nickel skeleton catalysts by derivatograph

The structure and properties of non-pyrophoric skeleton catalysts prepared from NiSi, NiAlSi, NiMg and NiZn alloys have been studied—apart from other thermal methods—by means of the derivatograph.Our experimental results have contributed to the explanation of the non-pyrophoric behaviour of these catalysts. We demonstrated that the desorption of the hydrogen content in our catalysts is not accompanied by the oxidation of active nickel. This oxidation takes place only at higher temperatures, above 200°C, at a rate proportional to the amount of active nickel.Other constituents of the catalysts (adsorbed water, hydroxide content) were also determined from the experimental data. The outstandingly high Mg(OH)₂ content of the NiMg catalyst indicates that its structure is dissimilar: Mg(OH)₂ also acts as support for the catalyst.     

Oxametallacycloalcanes : V. Synthese de sila-2, germa-2 et stanna-2 oxa-1 cyclopentanes par deshydrocondensation intramoleculaire d'hydrures silicies,germanies ou stanniques γ-hydroxyles

The γ-hydroxymetal hydrides

OH (M = Si, Ge, Sn) were synthesized by reduction of γ-acetoxychloro- or γ-hydroxychloro-silanes, -germanes and -stannanes. These derivatives with MH bonds lead, by cyclisation at room- or higher temperatures, with or without catalyst, depending on the nature of the metal, to various oxametallacyclopentanes. The cyclisation proceeds by intramolecular dehydrocondensation between MH and OH bonds. These dehydrocondensation reactions are analysed and discussed according to the polarity of the MH bonds. Intramolecular addition of the MH bond into the unsaturated carboncarbon bonds of the corresponding non-cyclic compounds is also an excellent way of preparing the same heterocycles.The IR and NMR analyses of all new compounds are given.     

Non-aqueous cerimetric determination of thioureas

Ammonium hexanitratocerate (in acetonitrile) solution has been used as an oxidimetric reagent for the visual and potentiometric determination of thiourea and its alkyl derivatives in acetonitrile medium. The thioureas are oxidized to their corresponding disulphides. The method is simple, accurate, reliable and widely applicable.