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  • 1
    Electronic Resource
    Electronic Resource
    Bildung siliciumorganischer Verbindungen. 111. Die Hydrierung Si-chlorierter, C-spiroverbrückter 2,4-Disilacyclobutane mit LiAlH4 und iBu2AlH. Der Zugang zum Si8C3H20 (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 127-135 
    Details
    ISSN: 0044-2313
    Keywords: The hydrogenation of Si-chlorinated, C-spiro-linked 2,4-disilacyclobutanes with LiAlH4 and iBu2AlH ; Access to (H3Si)2CH—SiH2—CH(SiH3)—SiH2—CH(SiH3)2 and Si8C3H20 ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation of Organosilicon Compounds. 111. The Hydrogenation of Si-chlorinated, C-spiro-linked 2,4-Disilacyclobutanes with LiAlH4 or iBu2AlH. The Access to Si8C3H20The hydrogenation of Si-chlorinated, C-spiro-linked 2,4-disilacyclobutanes containing C(SiCl3)2 terminal groups with LiAlH4 in Et2O proceeds under complete cleavage of the fourmembered rings and under elimination of one SiH3 group. Such, Si8C3Cl20 4 forms (H3Si)2CH—SiH2—CH(SiH3)—SiH2—CH(SiH3)2 4α, and even Si8C3H20 4a with LiAlH4 forms 4α. The hydrogenation of related compounds containing however CH(SiCl3) terminal groups similarly proceeds under ring cleavage but no SiH3 groups are eliminated. Such, (Cl3Si)CH(SiCl2)2CH(SiCl3) 41 forms (H3Si)2CH—SiH2—CH2(SiH3) 41α. However, in reactions with iBu2AlH in pentane neither the disilacyclobutane rings are cleaved nor are SiH3 groups eliminated. Only by this method Si8C3H20 is accessible from 4, Si6C2H16 3a from Si6C2Cl16 3 and Si4C2H12 41a from 41. C(SiCl3)4 cleanly produces C(SiH3)4.Based on the knowledge about the different properties of LiAlH4 and iBu2AlH in hydrogenation reactions of disilacyclo-butanes it was possible to elucidate the composition and the structures of the hydrogenated derivatives of the product mixture from the reaction of MeCl2Si—CCl2—SiCl3 with Si(Cu) [1] and to trace them back to the initially formed Si chlorinated disilacyclobutanes Si6C2Cl15Me 34, Si6C2Cl14Me2 35, Si8C3Cl19Me 36 and Si8C3Cl18Me2 37.Compound 4a forms colourless crystals of space group P1 with a = 799.7(6), b = 1263.6(12), c = 1758.7(14) pm, α = 103.33(7)°, β = 95.28(6)°, γ = 105.57(7)° and Z = 4.
    Notes: Si-chlorierte, C-spiroverbrückte 2,4-Disilacyclobutane mit C(SiCl3)2-Endgruppen, wie Si8C3Cl20 4, reagieren mit LiAlH4 in Et2O unter Spaltung der Vierringe und Abspaltung einer SiH3-Gruppe. So bildet 4 (H3Si)2CH—SiH2—CH(SiH3)—SiH2—CH(SiH3)2 4α. Ebenso reagiert Si8C3H20 4a zu 4α. (Cl3Si)CH(SiCl2)2CH(SiCl3) 41 (CHSiCl3-Endgruppen) reagiert unter Ringspaltung, aber ohne Abspaltung einer SiH3-Gruppe zu (H3Si)2CH—SiH2—CH2(SiH3) 41α. Dagegen erfolgen die Umsetzungen mit iBu2AlH in Pentan unter Erhalt der Ringgerüste und ohne Abspaltung einer SiH3-Gruppe. So bildet 4 das Si8C3H20 4a, 3 das Si6C2H16 3a, 41 das Si4C2H12 41a und C(SiCl3)4 das C(SiH3)4.Mit diesen Kenntnissen über die unterschiedlichen Eigenschaften von LiAlH4 und iBu2AlH bei der Hydrierung von Disilacyclobutanen war es möglich, die Zusammensetzung und die Strukturen der hydrierten Derivate aus dem Produktgemisch der Reaktion von MeCl2Si—CCl2—SiCl3 mit Si(Cu) [1] aufzuklären und auf die ursprünglich gebildeten Si-chlorierten Disilacyclobutane Si6C2Cl15Me 34, Si6C2Cl14Me2 35, Si8C3Cl19Me 36 und Si8C3Cl18Me2 37 zurückzuführen. 4a bildet farblose Kristalle und kristallisiert in der Raumgruppe P1; a = 799,7(6), b = 1263,6(12), c = 1758,7(14) pm, α = 103,33(7)°, β = 95,28(6)°, γ = 105,57(7)° mit Z = 4.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19946200121
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  • 2
    Electronic Resource
    Electronic Resource
    Komplexchemie P-reicher Phosphane und Silylphosphane. XII. Bildung und Struktur von Li(THF)2[η2-(tBu2P)2P], Li(TMEDA)[η2-(tBu2P)2P], Li(THF)2[η2-(iPr2P)2P], Li(THF)2[η2-(Et2N)2P—P—PtBu2], Li(THF)2[η2-(tBu2P—P—PiPr2] und (tBu2P)2P—SiMe3Professor Kurt Dehnicke zum 65. Geburtstag gewidmet (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 1564-1572 
    Details
    ISSN: 0044-2313
    Keywords: Li(THF)2[η2-(tBu2P)2P] ; Li(TMEDA)[η2-(tBu2P)2P] ; Li(THF)2[η2-(iPr2P)2P] ; Li(THF)2[η2-(Et2N)2P—P—PtBu2] ; Li(THF)2[η2-(tBu2P—P—PiPr2)] ; (tBu2P)2P—SiMe3 ; crystal structures ; 1H, 31P, 7Li-NMR spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation and Structure of Li(THF)2[η2-(tBu2P)2P], Li(TMEDA)[η2-(tBu2P)2P], Li(THF)2[η2-(iPr2P)2P], Li(THF)2[η2-(Et2N)2P—P—PtBu2], Li(THF)2[η2-(tBu2P—P—PiPr2] and (tBu2P)2P—SiMe3The formation and crystal structures of the compounds (tBu2P)2P—SiMe3 1, Li(THF)2[η2-(tBu2P)2P] 2, Li(TMEDA)[η2-(tBu2P)2P] 3, Li(THF)2[η2-(iPr2P)2P] 4, Li(THF)2[η2-(Et2N)2P—P—PtBu2] 5 and Li(THF)2[η2-(tBu2P—P—PiPr2)] 6 are reported. Compounds 3-6 are formed by reacting the corresponding silylated triphosphanes with nBuLi: 2 and 3 result from (tBu2P)2P—SiMe3 1, 4 from (iPrP)2P—SiMe3, 5 from (Et2N)2P—P(SiMe3)—PtBu2 and 6 from tBu2P—P(SiMe3)—PiPr2. 1 crystallizes in the orthorhombic space group P212121 (no. 19) with a = 910.87(7) pm, b = 1132.5(1) pm, c = 2373.5(2) pm (determined at 90 K). The structure determination of 2 was performed at 293 K and 200 K, respectively. 2 crystallizes in the monoclinic space group P21/n (no. 14) with a = 1069.7(3) pm, b = 1802.5(3) pm, c = 1604.0(7) pm, β = 98.11(2)° (200 K); 3 also in P21/n (no. 14) with a = 904.3(2) pm, b = 1936.4(5) pm, c = 1653.2(3) pm, β = 94.52(1)° (200 K). 4 crystallizes monoclinically in C2/c (no. 15) with a = 1650.0(5) pm, b = 945.6(3) pm, c = 1779.8(5) pm, β = 108.81(2)° (200 K); 5 in P21/n (no. 14) with a = 939.4(5) pm, b = 1736.8(6) pm, c = 1943.3(7) pm, β = 98.17(4)° (200 K). All compounds contain Z = 4 molecules in the unit cell.The 1H, 31P and 7Li NMR spectra of 2-6 are discussed.
    Notes: Es wird über die Verbindungen (tBu2P)2P—SiMe3 1, Li(THF)2[η2-(tBu2P)2P] 2, Li(TMEDA) · [η2-(tBu2P)2P] 3, Li(THF)2[η2-(iPr2P)2P] 4, Li(THF)2[η2-(Et2N)2P—P—PtBu2] 5 und Li(THF)2[η2-(tBu2P—P—PiPr2)] 6 berichtet. Letztere bilden sich durch Umsetzung der entsprechenden silylierten Triphosphane mit nBuLi: 2 und 3 aus (tBu2P)2P—SiMe3 1, 4 aus (iPr2P)2P—SiMe3, 5 aus (Et2N)2—P · (SiMe3)—PtBu2, 6 aus tBu2P—P(SiMe3)—PiPr2.1 kristallisiert orthorhombisch in P212121 (Nr. 19) mit a = 910,87(7) pm, b = 1132,5(1) pm, c = 2373,5(2) pm (bei 90 K bestimmt). Die Strukturbestimmung von 2 erfolgte bei 293 K und 200 K. 2 kristallisiert monoklin in P21/n (Nr. 14) mit a = 1069,7(3) pm, b = 1802,5(3) pm, c = 1604,0(7) pm, β = 98,11(2)° (200 K), 3 ebenfalls in P21/n (Nr. 14) mit a = 904,3(2) pm, b = 1936,4(5) pm, c = 1653,2(3) pm, β = 94,52(1)° (200 K). 4 kristallisiert monoklin in C2/c (Nr. 15) mit a = 1650,0(5) pm, b = 945,6(3) pm, c = 1779,8(5) pm, β = 108,81(2)° (200K), 5 in P21/n (Nr. 14) mit a = 939,4(5) pm, b = 1736,8(6) pm, c = 1943,3(7) pm, β = 98,17(4)° (200 K). Alle fünf Verbindungen enthalten jeweils vier Formeleinheiten in der Elementarzelle.Es wird über die Untersuchung der 1H-, 31P- und 7Li-NMR-Spektren der Verbindungen 2-6 berichtet.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220920
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