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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 515 (1984), S. 173-181 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Chalcogenolates. 141. Studies on Trimethylsilyl Xanthic Acid. 1. Synthesis and Properties of Trimethylsilyl XanthatesThe trimethylsilyl xanthates \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm M}\left[{{\rm S}_2 {\rm C} - {\rm OSi}\left({{\rm CH}_3} \right)_3} \right]\,{\rm mit\,M} = {\rm Li,Na,K},{\rm Rb},{\rm Cs} $$\end{document} have been prepared by reaction of the corresponding silanolate with carbon disulfide. The compounds were characterized by means of chemical and diverse spectroscopic methods.The existence of unstable trimethylsilyl xanthic acid has been demonstrated.
    Notes: Die Trimethylsilylxanthate \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm M}\left[{{\rm S}_2 {\rm C} - {\rm OSi}\left({{\rm CH}_3} \right)_3} \right]\,{\rm mit\,M} = {\rm Li,Na,K},{\rm Rb},{\rm Cs} $$\end{document} wurden durch Umsetzung des entsprechenden Silanolats mit Kohlenstoffdisulfid hergestellt und mit Hilfe chemischer und verschiedener spektroskopischer Methoden charakterisiert.Die Existenz der instabilen Trimethylsilylxanthogensäure konnte gesichert werden.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 515 (1984), S. 182-186 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Chalcogenolates. 142. Studies on Trimethylsilyl Xanthic Acid. 2. S-Methyl and S-Ethyl Trimethylsilyl XanthatesThe hitherto unknown S-alkyl trimethylsilyl xanthates (CH3)3SiO—CS—SR, where R = CH3 and C2H5, have been characterized with electron absorption, infrared, nuclear magnetic resonance (1H, 13C, and 29Si), and mass spectra.
    Notes: Die bisher nicht bekannten S-Alkyltrimethylsilylxanthate (CH3)3SiO—CS—SR mit R = CH3 und C2H5 wurden mit Hilfe von Elektronenabsorptions-, Infrarot-, 1H-, 13C- und 29Si-NMR- und Massenspektren charakterisiert.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 573 (1989), S. 75-88 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Chalcogenolates. 193. S-Bis(trimethylsilyl)amino Esters of Dithiocarbamic Acids. 2. Spectroscopic CharacterizationElectron absorption, infrared, and nuclear magnetic resonance spectra (1H, 13C, 29Si, 15N) of the title compounds RR′N—CS—S—N[Si(CH3)3]2 with R = R′ = CH3, C2H5, CH(CH3)2, CH2—C6H5 as well as with R = CH3 and R′ = C6H5 are communicated and discussed.Coupling constants have been determined (data see „Inhaltsübersicht“).For the compound with R = R′ = CH3 the free activation energy of the rotation barrier around the N—CS bond is ΔG* = 58 kJ/mol at -2°C (coalescence temperature).
    Notes: Elektronenabsorptions-, Infrarot- und Kernresonanzspektren (1H, 13C, 29Si, 15N) der Titelverbindungen RR′N—CS—S—N[Si(CH3)3]2 mit R = R′ = CH3, C2H5, CH(CH3)2, CH2—C6H5 sowie mit R = CH3 und R′ = C6H5 werden mitgeteilt und diskutiert.Folgende Kopplungskonstanten wurden ermittelt (R = R′ = CH3):\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} ^{\rm 1} {\rm J}\left({{}^{\rm 1}{\rm H} - {}^{12}{\rm C}} \right) = 119{\rm Hz},{}^2{\rm J}({}^1{\rm H} - {}^{29}{\rm Si} = 6,5{\rm Hz}, \\ ^{\rm 1} {\rm J}\left({{}^{{\rm 13}}{\rm C} - {}^{12}{\rm Si}} \right) = 57,7{\rm Hz},{}^2{\rm J}({}^{13}{\rm C} - {}^{15}{\rm N} = 1,97{\rm Hz}, \\ ^{\rm 1} {\rm J}\left({{}^{{\rm 29}}{\rm Si} - {}^{15}{\rm N}} \right) = 8,97{\rm Hz},{}^3{\rm J}({}^{15}{\rm N} - {}^1{\rm H)} \approx 0,5{\rm Hz}{\rm .} \\ \end{array} $$\end{document}Für die Verbindung mit R = R′ = CH3 beträgt die freie Aktivierungsenergie der Rotationsbarriere um die N—CS-Bindung ΔG* = 58 kJ/mol bei der Koaleszenztemperatur (-2°C).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 579 (1989), S. 129-133 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Chalcogenolates. 195. Attempts to Prepare Derivatives of N,N-Bis (trimethylsilyl)-dithiocarbamic AcidThe reaction of alkali metal bis(trimethylsilyl)amides with CS2 in ether at lower temperatures produces the corresponding N, N-bis(trimethylsilyl)dithiocarbamate M[S2C—N(SiMe3)2] with M = Na, K. The esters (Me3Si)2N—CS—SR, where R = CH3 and C2H5, have been obtained by reaction of the dithiocarbamates with alkyl iodide as well as by reacting chlorodithioformic acid S-esters with sodium bis(trimethylsilyl)amide. The sodium salt reacts in acetone at -20°C with HCl(g) to form the acid (Me3Si)2N—CS—SH.The existence of the yellow, very unstable compounds has been demonstrated by means of l3C-NMR spectra and mass spectra. The esters decompose to yield trimethylsilyl isothiocyanate.
    Notes: Alkalimetall-bis(trimethylsilyl)amide reagieren mit CS2 in Ether bei tieferen Temperaturen unter Bildung des entsprechenden N, N-Bis(trimethylsilyl)dithiocarbamats M[S2C—N(SiMe3)2] mit M = Na, K. Die Alkylester (Me3Si)2N—CS—SR mit R = CH3, C2H5 wurden sowohl durch Umsetzung der Dithiocarbamate mit Alkyliodid als auch durch Reaktion von Chlordithioameisensäure-S-alkylestern mit Natrium-bis(trimethylsilyl)amid bei tiefen Temperaturen gewonnen. Die Reaktion der Na+-Verbindung mit HCl(g) in Aceton bei -20°C führt zu der Säure (Me3Si)2N—CS—SH.Die Existenz dieser gelben, sehr instabilen Verbindungen wurde mit Hilfe von 13C-NMR- und Massenspektren bewiesen. Die Ester zersetzen sich unter Bildung von Trimethylsilylisothiocyanat.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 572 (1989), S. 126-134 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Chalcogenolates. 192. S-Bis(trimethylsilyl)amino Esters of Dithiocarbamic Acids. 1. Synthesis and PropertiesThe title compounds RR′N—CS—S—N[Si(CH3)3]2, where R = R′ = CH3, C2H5, CH(CH3)2, CH2—C6H5, and with R = CH3 and R′ = C6H5 have been prepared by three procedures: by splitting the S—S bond of disulfanes [RR′N—CS—]2S2 with Na[N(Si(CH3)3)2] and with [(CH3)3Si]2N—MgBr as well as by reaction of Na[S2C—NRR′] with BrN[Si(CH3)3]2. The yields are compared.Physical and chemical properties are described, mass spectra are given.
    Notes: Die Titelverbindungen RR′N—CS—S—N[Si(CH3)3]2 mit R = R′ = CH3, C2H5, CH(CH3)2 und CH2—C6H5 sowie mit R = CH3 und R′ = C6H5 wurden nach drei Verfahren hergestellt: durch Spaltung der S—S-Bindung von Disulfanen [RR′N—CS—]2S2 mit Na[N(Si(CH3)3)2] und mit [(CH3)3Si]2N—MgBr sowie durch Reaktion von Na[S2C—NRR′] mit BrN[Si(CH3)3]2. Die Ausbeuten werden verglichen.Physikalische und chemische Eigenschaften sowie Massenspektren werden mitgeteilt.
    Additional Material: 5 Tab.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 575 (1989), S. 129-136 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bis[bis(trimethylsilyl)amino]sulfane. 2. Crystal and Molecular StructureThe title compound [(CH3)3Si]2N—S—N[Si(CH3)3]2 crystallizes with Z = 4 in the monoclinic space group A2/a (Nr. 15) with cell dimensions a = 22.436(4) Å, b = 6.434(5) Å, c = 17.089(6) Å, β = 117.66(2)º. For 5091 independent reflections, measured at -80°C, the structure could be refined to R = 0.079 and Rw = 0.120.The molecules are linked together by van der Waals interactions and form layers in the bc plane, in agreement with the observed cleavage along (100).
    Notes: Die Titelverbindung [(CH3)3Si]2N—S—N[Si(CH3)3]2 kristallisiert monoklin mit Z = 4 in der Raumgruppe A2/a (Nr. 15) mit den Gitterdimensionen a = 22,436(4) Å, b = 6,434(5) Å, c = 17,089(6) Å, β = 117,66(2)º. Unter Verwendung von 5091 symmetrieunabhängigen Reflexen, gemessen bei -80°C, konnte die Struktur bis auf Zuverlässigkeitsfaktoren von R = 0,079 und Rw = 0,120 verfeinert werden.Im Kristallverband werden die Moleküle durch van-der-Waals-Wechselwirkungen zusammengehalten und bilden Schichten in der bc-Ebene, in Übereinstimmung mit der makroskopischen Spaltbarkeit parallel (100). In der Molekel beträgt der Winkel N—S—N 109,6(1)º.
    Additional Material: 3 Ill.
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