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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3017-3024 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Redox Reactions between Tri-tert-butylphosphine and Element(IVb)-Tetrachlorides: Tri-tert-butylchlorophosphonium SaltsTri-tert-butylphosphine reacts with equimolare amounts of germaniumtetrachloride or tintetrachloride yielding new compounds with the formula (t-C4H9)3PMCl4 (M=Ge, Sn). The Comparison of n. m. r., infrared-, and raman spectra as well as the conductivities with the corresponding data of tri-tert-butyldichlorophosphorane, prepared, using tri-tert-butylphosphine and Chlorine, indicates, that all these compounds are tri-tert-butylchlorophosphine salts. Tri-tert-butyl-chlorophosphonium salts are also available, by the reaction of tri-tert-butyldichlorophosphorane with various element chlorides.
    Notes: Tri-tert-butylphosphin reagiert mit Germaniumtetrachlorid und Zinntetrachlorid im Molverhältnis 1:1 zu neuen Verbindungen der Zusammensetzung (t-C4H9)3PMCl4 (M=Ge, Sn). Der Vergleich von Kernresonanz- und Schwingungsspektren sowie von Leitfähigkeiten mit den entsprechenden Daten von Tri-tert-butyldichlorphosphoran, das aus Tri-tert-butylphosphin mit elementarem Chlor erhalten wurde, zeigt, daß die Verbindungen als Tri-tert-butylchlor-phosphonium-Salze vorliegen. Weitere Verbindungen dieses Typs sind aus Tri-tert-butyldichlor-phosphoran mit verschiedenen Elementchloriden zugänglich.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 2267-2272 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Complex-bound Carbene Analogues, II: Synthesis and Vibrational Spectra of Pentacarbonyl[chloro(di-tert-butylphosphino)stannio]-metal(VI A) ComplexesThe tindichloride complexes pentacarbonyl(dichlorotetrahydrofurane-stannio)chromium(0) (1), -molybdenum(0) (2) and -tungsten(0) (3) react with di-tert-butyl(trimethylsilyl)phosphine with elimination of tetrahydrofurane and formation of chlorotrimethylsilane to give the new, base free stannio complexes (CO)5M—Sn(Cl)[P(tBu)2] (4-6: M = Cr, Mo, W) with 75 to 85% yield. The ligand properties of chloro(di-tert-butylphosphino)-stannandiyl (-stannylene) are discussed on the basis of infrared and Raman data, and other physical properties.
    Notes: Die SnCl2-Metallkomplexe Pentacarbonyl(dichlortetrahydrofuran-stannio)chrom(0) (1), -molybdän(0) (2) und -wolfram(0) (3) reagieren mit Di-tert-butyl(trimethylsilyl)phosphin unter Verdrängung von Tetrahydrofuran und Eliminierung von Chlortrimethylsilan, wobei die neuen basenfreien Stannylenkomplexe (CO)5M—Sn(Cl)[P(tBu)2] (4-6: M = Cr, Mo, W) in 75-85 proz. Ausbeute erhalten werden. Die Ligandeneigenschaften von Chlor(di-tert-butylphosphio)stanandiyl (-stannylen) werden anhand von IR- und Raman-Daten sowie der physikalischen Eigenschaften von Ligand und Komplexen diskutiert.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 108 (1975), S. 2261-2268 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chlor(organogermyl)phosphineDi-tert-butyl(trimethylsilyl)phosphine reacts with dichlorodimethylgermane, trichloromethylgermane, and germanium tetrachloride to form di-tert-butyl(chlorodimethylgermyl)phosphine (5), di-tert-butyl(dichloromethylgermyl)phosphine (6), and di-tert-butyl(trichlorogermyl)phosphine (7) in high yields. Similarly diphenyl(trimethylsilyl)phosphine and tris(trimethylsilyl)phosphine react with dichlorodimethylgermane to yield new (chlorodimethylgermyl)phosphines (3,8). The vibrational and n.m.r. spectra of the new compounds are discussed.
    Notes: Di-tert-butyl(trimethylsilyl)phosphin reagiert mit Dichlordimethylgerman, Trichlormethylgerman und Germaniumtetrachlorid in hohen Ausbeuten zu Di-tert-butyl(chlordimethylgermyl)phosphin(5), Di-tert-butyl(dichlormethylgermyl)phosphin (6) und Di-tert-butyl(trichlorgermyl)phosphin (7). Entsprechend reagieren Diphenyl(trimethylsilyl)phosphin und Tris(trimethylsilyl)phosphin mit Dichlordimethylgerman zu neuen (Chlordimethylgermyl)phosphinen (3,8). Schwingungsspektren und Kernresonanzspektren der neuen Verbindungen werden diskutiert.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 237-245 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organo[chloro(methyl)stannyl]phosphines and -aminesEquimolar amounts of di-tert-butyl(trimethylsily)phosphine (1) and dichlorodimethylstannane or trichloro(methyl)stannane react with formation of di-tert-butyl(chlorodimethylstannyl)phosphine (2) and di-tert-butyl[dichloro(methyl)stannyl]phosphine (3), respectively. The reaction of 1 with trichloro(methyl)stannane in a molar ratio of 2:1 yields chloro(methyl)stannanediylbis(di-tert-butylphosphine)(4). All experiments to synthesize he analogous (chlorodimethylstannyl)diphenyl-phosphine failed. A new method for the synthesis of (chlorodimethylstannyl)diethylamine (6) and (bromodimethylstannyl)diethylamine (7) was found with the reaction of bis(diethylamino)dimethylstannane with chloro- and bromotrimethylsilane, respectively. The i. r. and 1H n.m.r. spectra are discussed.
    Notes: Äquimolare Mengen von Di-tert-butyl(trimethylsilyl)phosphin (1) und Dichlordimethylstannan bzw. Trichlor(methyl)stannan reagieren unter Bildung von Di-tert-butyl(chlordimethylstannyl)-phosphin (2) und Di-tert-butyl[dichlor(methyl)stannyl]phosphin (3). Die Umsetzung von 1 mit Trichlor(methyl)stannan im Molverhältnis 2:1 führt glatt zu Chlor(methyl)stannandiylbis(di-tert-butylphosphin) (4). Die Versuche, ein entsprechendes (Chlordimethylstanny)diphenyl-phosphin zu synthetisieren, schlugen dagegen fehl. Diäthyl(chlordimethylstannyl)amin (6) und Diäthyl(bromdimethylstannyl)amin (7) werden durch Spaltung von Bis(diäthylamino)dimethylstannan mit Chlor- bzw. Bromtrimethylsilan dargestellt. IR- und NMR-Spektren werden diskutiert.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3419-3425 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Triorganophospine-dichlorogermylenesTriphenylphosphine, triethylphosphine and tri-tert-butylphosphine react with equimolar amounts of germaniumdichloride.dioxane yielding triorganylphosphine-dichlorogermylenes R3PGeCl2 (R=C2H5, C6H5, t-C4H9). With tri-n-butylphosphine only a mixture of dioxane-stabilized and phosphine-stabilized GeCl2 was obtained. Formation and properties as well as n. m. r., infrared and raman spectra of the new compounds are discussed.
    Notes: Triphenylphosphin, Triäthylphosphin und Tri-tert-butylphosphin reagieren mit dem Germanium-dichlorid-Dioxan-Komplex unter Verdrängung von Dioxan zu den Triorganylphosphin-dichlorgermylenen R3PGeCl2 (R=C2H5, C6H5, t-C4H9). Mit Tri-n-butylphosphin wird lediglich ein Gemisch von dioxanstabilisiertem und phosphinstabilisiertem GeCl2 erhalten. Bildungsweise und Eigenschaften sowie 1H-NMR-, 31P-NMR-, infrarot- und ramanspektroskopische Daten der Verbindungen werden diskutiert.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1045-1049 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dimeric Phospha- and Thiastannylenes: Ylide-type Diphospha- and DithiadistannetanesBis(di-tert-butylphosphino)tin(II) (1) is obtained from the reaction of potassium di-tert-butyl-phosphide with stannous chloride or with the stannous chloride-triethylphosphane complex. Bis(tert-butylthio)tin(II) (2) is prepared by reaction of (η5-C5H5)2Sn with 2-methyl-2-propanethiol or from stannous chloride and (tert-butylthio)trimethylsilane. In solution, 1 and 2 are PR2-and SR-bridged dimers, respectively. NMR spectra indicate that rapid scrambling of terminal and bridging substituents occurs in 2 but not in the cyclic \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm P}\limits^ + - \mathop {\rm S}\limits^{\rm - } {\rm n} $\end{document} ylide 1.
    Notes: Bis(di-tert-butylphosphino)zinn(II) (1) entsteht durch Reaktion von Kalium-di-tert-butylphos-phid mit Zinndichlorid oder dem Zinndichlorid-Triethylphosphan-Komplex. Bis(tert-butylthio)-zinn(II) (2) wird hergestellt durch Umsetzung von (η5-C5H5)2Sn mit 2-Methyl-2-propanthiol und entsteht auch bei der Reaktion von Zinndichlorid mit (tert-Butylthio)trimethylsilan. 1 und 2 liegen in Lösung als PR2- bzw. SR-verbrückte Dimere vor. Kernresonanzspektren zeigen, daß bei dem cyclischen \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm P}\limits^ + - \mathop {\rm S}\limits^{\rm - } {\rm n} $\end{document}-Ylid 1 im Gegensatz zu 2 auch in Ethern keine raschen Platzwechselvorgänge (Brücke/terminal) ablaufen.
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  • 7
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Properties of Tellurium-Tellurium Bonds, VI.  -  Structure and Barrier of Interconversion of Enantiomeric Conformations of Bis(2,4,6-tri-tert-butylphenyl)ditellaneOxidation of lithium (2,4,6-tri-tert-butylphenyl)telluride provides red and strong refractive needles of bis(2,4,6-tri-tert-butylphenyl)-ditellane (1) which crystallize monoclinically in the space group C2/c. The bond distance d(Te-Te), the bond angle at the Te atoms, and the torsion angle at the Te-Te bond were found to be 271.3 pm, 100.6°, and 92.1°, respectively. The C2 symmetry of the molecule gives rise to different chemical surroundings for both tert-butyl groups in ortho position belonging to the aryl groups. This effect can also be observed in solution at low temperatures. For the first time, dynamic NMR spectroscopy succeeded in determination of the barrier of rotation about a Te-Te bond. This barrier was found to be 40.9 kJ · mol-1 and is 20% less than that in the corresponding diselane.
    Notes: Bis(2,4,6-tri-tert-butylphenyl)ditellan (1) wird durch Oxidation von Lithium-(2,4,6-tri-tert-butylphenyl)tellurid in Form roter, stark lichtbrechender Kristalle erhalten. 1 kristallisiert monoklin in der Raumgruppe C2/c. Der Bindungsabstand d(Te-Te) beträgt 271.3 pm, der Bindungswinkel an den Te-Atomen 100.6° und der Torsionswinkel an der Te-Te-Bindung 92.1°. Durch die C2-Symmetrie besitzen die beiden ortho-ständigen tert-Butylgruppen der Substituenten unterschiedliche chemische Umgebung, die auch in Lösung bei tiefen Temperaturen erkennbar wird. Aus NMR-spektroskopischen Daten gelang erstmals die Bestimmung der Rotationsbarriere um eine Te-Te-Bindung; sie beträgt 40.9 kJ · mol-1. Dieser Wert ist um 20% kleiner als für das entsprechende Diselan.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 2109-2110 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Iodo[tris(trimethylsily)methyl]selane: Synthesis of the First Alkylselenenyl IodideBis[tris(trimethylsilyl)methyl]diselane (1) reacts with elemental iodine to provide iodo[tris(trimethylsilyl)methyl]selane (2) in high yield. 2 is the first iodoselane that does not suffer from redismutation equilibria in solution at ambient temperature with iodine and the parent diselane.
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  • 9
    ISSN: 0009-2940
    Keywords: Trichlorosilylation ; Chlorophosphanes ; Silylphosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of Silicon-Silicon Bonds, 2[1]. - Trichlorosilylations of tert-Butyldichlorophosphane and tert-Butylbis(trimethylsilyl)phosphane with Hexachlorodisilane: Synthesis of New Bifunctional (Trichlorosilyl)phosphanesDi-tert-butyl(trimethylsilyl)phosphane (1) and tert-butylbis(trimethylsilyl)phosphane (3) react with one equivalent of hexachlorodisilane with exchange of one trimethylsilyl group by a trichlorosilyl group under mild conditions to give di-tert-butyl(trichlorosilyl)phosphane (2) and tert-butyl(trichlorosilyl)(trimethylsilyl)phosphane (4) in fair yields. tert-Butylbis(trichlorosilyl)phosphane (5) is available from tert-butyldichlorophosphane without organometallic reagents and solvents by simple reductive trichlorosilylation with the help of two equivalents of hexachlorodisilane. 5 is a useful precursor for phosphaalkane synthesis: with pivaloyl chloride, 5 leads to tert-butyl-[tert-butyl(trichlorosilyloxy)methylene]phosphane (6). From 4 with pivaloyl chloride mainly 6 and some known tert-butyl[tert-butyl(trimethylsilyloxy)methylene]phosphane (7) are formed.
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  • 10
    ISSN: 0009-2940
    Keywords: Reductive silylation ; Aminochlorophosphanes ; Silylphosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of alkyl(diorganylamino)chlorophosphanes R(R2′N)PCl 1 (1a: R = tBu, R′ = Et, 1b: R = iPr, R′ = iPr; 1c: R = iPr, R′ = Ph) with hexachlorodisilane, afforded alkyl(diorganylamino)trichlorosilylphosphanes R(R2′N)PSiCl3 2 (2a: R = tBu, R′ = Et; 2b: R = iPr, R′ = iPr; 2c: R = iPr, R′ = Ph) and silicon tetrachloride. An intermediate formed in the reaction of 1b with hexachlorodisilane, the adduct iPr(iPr2N)(Cl)P-Si(Cl)3-SiCl3 (3b = 1b · Si2Cl6), was detected by 31P- and 29Si-NMR spectra that indicate pentacoordinated silicon bound to tetracoordinated phosphorus and tetracoordinated silicon. Trichlorosilylphosphanes 2 are also available from 1 under very mild conditions by reductive trichlorosilylation with trichlorosilane in the presence of triethylamine. Compounds 2 were identified analytically, by mass spectroscopy, multinuclear NMR, and an X-ray structure determination of 2c.
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