Hydroxidgruppen an Zeolithen. II. Zahl und Eigenschaften von Hydroxidgruppen an CeNaY- und HNaY-Zeolithen unterschiedlichen Austauschgrades

Hydroxide Groups on Zeolites. II. Number and Properties of Hydroxide Groups on CeNaY and HNaY Zeolites of Different Exchange Degree The number of hydroxide groups on CeNaY and HNaY zeolites was examined by D₂ exchange, and their properties in dependence of the cation exchange degrees were studied by IR spectroscopy. On CeNaY zeolites there exist six kinds and on HNaY zeolites at least seven kinds of hydroxide groups. On the CeNaY zeolites, the hydroxide groups are produced by dissociative chemisorption of water on Ce³⁺ ions. Their total number increases continuously with increasing exchange degree. Some of the hydroxide groups are acid BRÖNSTED centers whose number increases with increasing exchange degree and decreases with the temperature of preheating increasing to about 600°C. On the HNaY zeolites, the hydroxide groups are produced by thermal decomposition of the NH⁺₄ ions, by dealumination and interaction of the Al³⁺ ions produced in this way in the place of cations with water. Above the threshold value of 35% the total number of the hydroxide groups increases very rapidly with increasing exchange degree. One part of the hydroxide groups decreasing with increasing exchange degree acts as acid BRÖNSTED centers. The number of these centers does not decrease until at preheating temperatures above 450°C.     

Hydroxidgruppen an Zeolithen. III. Eigenschaften von Hydroxidgruppen an ZnNaY-, CuNaY-, NiNaY- und CrNaY-Zeolithen

Hydroxide Groups on Zeolites. III. Properties of Hydroxide Groups on ZnNaY, CuNaY, NiNaY, and CrNaY Zeolites The properties of hydroxide groups in dependence on the degree of exchange were studied by IR spectroscopy of ZnNaY, CuNaY, NiNaY, and CrNaY zeolites. Five kinds of hydroxide groups occur on these zeolites: Hydroxid groups limiting the lattice, 3 kinds of structural hydroxide groups, and MeOH⁺ groups. These are the same kinds of hydroxide groups as exist on alkaline earths-Y-zeolites. Some of the OH groups act as acid Brönsted centers. The number of acid Brönsted centers reaches maximum values at degrees of exchange of 40–50% after a pretreatment at 300–400°C. The zeolitic structure is partially destroyed in ZnNaY, CuNaY, and especially CrNaY, at high degree of exchange.     

Katalytische Eigenschaften von Zeolithen in der Seltenerdmetallionenform

Ohne Zusammenfassung     

Zersetzung von n- und sek.-Butylacetat an synthetischen Zeolithen

Ohne Zusammenfassung     

Bildung und Eigenschaften von Acylphosphinen. I. Monosubstitutionsreaktionen an substituierten Disilylphosphinen mit Pivaloylchlorid

Formation and Properties of Acylphosphines. I. Mono Substitution Reactions of Substituted Disilylphosphines with Pivalie Chloride Between ?30°C and ?10°C one trimethylsilyl group of substituted bis(trimethy1-sily1)phosphines is replaced by the acgl moiety in the reaction Rith pivalic chloride. The keto forms are thermally labile arid rearrange with migration of the silyl group from phosphorus to oxygai just below room temperature. The new compounds (enol forms) we stable in the absence of moisture and air and show an unusual structure with a P? C double bond. The spectroscopic properties are discussed.     

Trimethylsilylverbindungen der Vb-Elemente. I Synthese und Eigenschaften von Trimethylsilylarsanen

Trimethylsilyl Derivatives of Vb-Elements. I. Syntheses and Properties of Trimethylsilylarsanes Chlorotrimethylsilane and ?Na₃As/K₃As”? prepared from a sodium potassium alloy and arsenic powder in dimethoxyethane form tris(trimethylsilyl)arsane 4 in 80 to 90percent; yield. 4 reacts with methyllithium in THF or dimethoxyethane to lithiumbis(trimethylsilyl)arsenide 5 , which crystallizes with two molecules THF – 5a – or one molecule dimethoxyethane – 5b – per formula unit. The latter adduct is dimeric in benzene. In the reaction of 5 with primary and secondary alkyl halides methyl- 1a , ethyl- 1b , isopropyl- 1c , benzyl- 1d , diphenylmethylbis(trimethylsilyl)arsane 1e and bis[bis(trimethylsilyl)arsano]methane 1f are formed. With tert. butyl chloride a β-elimination results in the formation of bis(trimethylsilyl)arsane; in the reaction with chlorodiphenylmethane and dibromoethane an alkali metal-halogen-exchange takes place yielding tetrakis(trimethylsilyl)-diarsane 6 . On heating bis[bis(trimethylsilyl)arsano]dimethylsilane 7 , synthesized from 5 and dichlorodimethylsilane, to 240°C for several days it decomposes to 4 and dodecamethyl-hexasila-tetra-arsa-adamantane 8 . Tert. butyl- 1g and phenylbis(trimethylsilyl)arsane 1h which cannot be obtained from 5 are prepared from primary arsanes via the corresponding dilithium derivatives.     

Struktur und Eigenschaften von Gd3I3C

Structure and Properties of Gd₃I₃C . The compound Gd₃I₃C is prepared by reaction of Gd, GdI₃ and C (2:1:1 mole) at 1 250 K in sealed Ta tubes. It is obtained as bronze-coloured needles which are air and moisture sensitive. The structure of Gd₃I₃C contains twin chains of C centered Gd₆ octahedra surrounded by I atoms capping all free edges like in the M₆X₁₂ cluster. The one-dimensional units are oriented along [010] and linked according to (GdGd_1/3Gd_2/2Gd_2/3C)₂IIII. Gd₃I₃C is metallic in the temperature range 300 K ≥ T ≥ 120 K, between 120 and 15 K the electrical resistance increases by 6 orders of magnitude. At high temperatures the susceptibility follows the Curie-Weiß law with a paramagnetic Curie temperature θ ≈ - 340 K. Two local maxima in the susceptibility at 100 K and 25 K indicate successive formation of antiferromagnetically ordered structures.     

Herstellung und Eigenschaften von Aluminiumaquoxid. I. Böhmit aus Aluminiumnitrat und Ammoniakwasser

Preparation and Properties of Aluminium Hydroxide. I. Boehmite from Aluminium Nitrate and Ammonia The physical-chemical properties of mainly boehmite containing aluminium hydroxide are studied which were made by continuous precipitation from aluminium nitrate solution with ammonia liquor using technical raw materials and test conditions being very similar to those applied in production. The influence of the precipitation conditions (pH value, temperature, concentration and residence time in the precipitation solution) on the composition, structure and texture of the precipitation products is investigated and information about their effect on the filtration behaviour are given. In the case of a continuous precipitation it is possible to obtain phase-pure boehmite being relatively well crystallised. The crystallinity and dispersity of the precipitated hydroxide determine their filterability and the cavity structure.     

Bildung und morphologische Eigenschaften von Schwefel an Viskosefasern

Ohne Zusammenfassung     

Darstellung und Eigenschaften von Carbonylisocyanat

Zusammenfassung Es wird über die erstmalige Darstellung von Carbonylisocyanat, CO(NCO)₂, durch thermische Zersetzung von Trichlorisocyanursäure berichtet; einige physikalische Eigenschaften der neuen Verbindung werden mitgeteilt. Ihre Reaktionen mit Alkali, Wasser, Ammoniak und Äthanol wurden untersucht. Durch Reaktion mit Wasser im Verhältnis 1: 1 wurde 2,4,6-Trioxo-tetrahydro-1,3,5-oxadiazin bzw. Carbonyldicarbamidsäureanhydrid als neue Verbindung erhalten.

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Carbonyl isocyanate has been prepared the first time by thermolysis of trichlorisocyanuric acid and some of its physical properties have been determined. Its reactions with alkali, water, ammonia and ethanol have been investigated. By reaction with equimolar amounts of water the novel compound 2,4,6-trioxotetrahydro 1,3,5-oxadiazine (carbonyl-dicarbamic acid anhydride) was obtained.

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Auszugsweise vorgetragen auf der Vortragstagung des VOeCh. am 28. 9. 1965 in Graz.     

Darstellung und Eigenschaften von Trifluormethylmercaptothiophosphoryldichlorid

Preparation and Properties of Trifluoromethylmercaptothiophosphoryldichloride The reaction of CF₃SP(O)Cl₂ with SPCl₃ leads to a CF₃S-chlorine exchange and gives CF₃SP(S)Cl₂ in 50% yield. A controlled hydrolysis of CF₃SP(O)Cl₂ affords CF₃SP(O)(OH)₂, that cannot be isolated as such, but it condenses to CF₃SP(O)(OH)O? [P(SCF₃)(O)? O]_nP(O)(OH)SCF₃. On the other hand, CF₃SP(S)Cl₂ reacts with water to yield H₃PO₄, CF₃SH, S₈, and HCl. CF₃SP(X)Cl₂ reacts with alcohols to give CF₃SP(X)(OR)₂ [R = CH₃, C₂H₅, n-C₃H₇, CH(CH₃)₂, n-C₄H₉ and for X = O, R = C₆H₅, too]. The formation of semi-esters CF₃SP(X)Cl(OR′) could be proven for X = O, R′ = CH₃, C₆H₅ and for X = S, R′ = R. While CF₃SP(O)(OC₂H₅)₂ rapidly decomposes into SCF₂ and FP(O)(OC₂H₅)₂, the other compounds and primarily CF₃SP(O)(OCH₃)₂ and CF₃SP(S)(OR)₂ ar stable. The reaction between CF₃SCl and CH₃SPCl₂ results in CF₃SCH₂SPCl₂ and that between CF₃SP(O)Cl₂ and AlCl₃ gives [CF₃SP(O)Cl]⁺[AlCl₄]^?. Physical and spectroscopical data are given for the newly formed compounds.     

Darstellung und Eigenschaften von Phenyljodcyclopentasilanen

Zusammenfassung Dekaphenylcyclopentasilan reagiert mit wasserfreiem HJ im Bombenrohr unter Benzolabspaltung zu Phenyljodcyclopentasilanen. Der Grad der Phenylabspaltung hängt von der Reaktionszeit ab. Reaktion mit Methanol führt zu entsprechenden Methoxyphenylcyclopentasilanen.Die Hydrolyse ergibt gelbe, fluoreszierende, polymere Hydrolysenprodukte, in denen Si₅-Ringe über Sauerstoff verknüpft sind. Die Farbe der Hydrolysenprodukte wird im Zusammenhang mit den Ergebnissen der Siloxenchemie diskutiert.

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Synthesis and properties of phenyliodocyclopentasilanes

Decaphenylcyclopentasilane reacts with anhydrous HJ in a sealed tube to give phenyliodocyclopentasilanes and benzene, and the degree of phenyl cleavage was found to depend on the reaction time. The corresponding methoxyphenylcyclosilanes are obtained in the reaction with methanol. Hydrolysis yields a yellow, fluorescent, polymeric compound containing Si₅-rings coupled by oxygen. The colour of the hydrolysis products is discussed in connection with pertinent results in siloxene chemistry.

     

Darstellung und Eigenschaften von Organoindiumbromiden

Synthesis and Properties of Organoindium Bromides i-Pr₃In gives with InBr₃ (molar ratio 2:1, toluene, 50°C) i-Pr₂InBr ( 1 ) and (molar ratio 1:2, toluene, 80°C) i-PrInBr₂ ( 2 ). The corresponding reaction of (PhCH₂)₃In and InBr₃ (2:1) gives (PhCH₂)₂InBr ( 3 ), while PhCH₂InBr₂ could be isolated only as ether adduct [PhCH₂InBr₂(OEt₂)_n] ( 4 ). With DME/MeCN and 2 and 4 with THF, respectively, yields the solvate complexes [InBr₃(DME)(MeCN)] ( 5 ), [i-PrInBr₂(THF)₂] ( 6 ) and [PhCH₂InBr₂(THF)₂] ( 7 ). The compounds 1–7 were investigated with NMR-, IR- and MS-techniques. Pyrolysis of the raw material of i-Pr₃In, which contains “MgBrCl” and additional treatment with Et₂O yields the salt [Mg₃Cl_4,65Br_0,35(Et₂O)₆][i-PrInBr_2,7Cl_0,3] ( 8 ). The cation, a trinuclear magnesium complex, possesses local D_3h-symmetric of the Mg₃X₅ backbone (X = Cl, Br).     

Darstellung und Eigenschaften von Methyl-methoxydisilanen

Zusammenfassung Methoxymethyldisilane werden durch Alkoholyse von Chlormethyldisilanen, bzw. durch Reaktion von Methoxychlorsilanen mit Trimethylsilyllithium hergestellt und näher charakterisiert. Auch bei diesen Verbindungen zeigt sich der schon früher beschriebene Einfluß des Sauerstoffs auf die Si–Si-Bindung, die durch die zusätzliche Elektronenbelastung des Siliciums durch die Elektronen des Sauerstoffs verstärkt wird.

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Methoxy methyl disilanes where prepared by means of alcoholysis of chloromethyl disilanes, or by reaction of methoxy chlorosilanes with trimethyl silyl lithium. These compounds also exhibit the already described influence of the oxygen upon the Si–Si bonding, which results in a strengthening of the bond by the electrons made available through the oxygen.

     

Darstellung und Eigenschaften von Tetracyanmethan

Zusammenfassung Tricyanmethylsilber reagiert mit Chlorcyan unter Bildung von Tetracyanmethan und AgCl. Das erstmals beschriebene Tetracyanmethan ist kristallin, sublimiert bei 60° im Vak., zersetzt sich ab 160° und ist in polaren Lösungsmitteln löslich. Das IR-Spektrum wird diskutiert und eine Zuordnung der Normal-schwingungen für T_d-Symmetrie getroffen. Die Hydrolyse in saurem und alkalischem Medium und die Reaktion mit LiCl werden beschrieben.

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Preparation and Properties of Tetracyanomethane

The reaction of silver tricyanomethanide with cyanogen chloride yields the hitherto unreported tetracyanomethane and AgCl. Tetracyanomethane is a crystalline solid, sublimes at 60° in vacuo, decomposes above 160° and is soluble in polar solvents. The IR spectrum is discussed and an assignment of the fundamental frequencies based on T_d symmetry is made. Hydrolysis with acid or alkali and the reaction with LiCl are described.

     

Darstellung und Eigenschaften von Aminodisilanen

Zusammenfassung Aus der Klasse der teilweise substituierten Aminodisilane wurden vier Vertreter der Dimethylaminomethyldisilane erstmals hergestellt und durch Analyse, Molrefraktion, UV-,¹H-NMR-, IR- und Ramanspektren charakterisiert.

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Preparation and properties of amino disilanes

Four dimethylamino-methyldisilanes have been prepared and characterized by analysis, molar refraction, UV,¹H-NMR, IR and Raman spectra.

     

Darstellung und Eigenschaften von Trinorbornylbor-Verbindungen

Synthesis and Properties of Trinorbornyl Boron Compounds Tris(1-norbornyl), Tris(2-norbornyl), and Tris(7-norbornyl) boron were synthesized from boron trifluoride diethylether and 1-norbornyl lithium or 2- and 7-norbornyl magnesium halides respectively. The compounds were characterized by the IR-, ¹³C-, ¹¹B-NMR, and mass spectra. Furthermore 1-norbornyl lithium was isolated in the crystalline state and investigated in detail.