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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 601 (1991), S. 111-119 
    ISSN: 0044-2313
    Keywords: Sulfonyl amines ; bis(dimesylamino)dimethyl silane ; bis(dimesylamino)dimethyl stannane ; preparation ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polysulfonyl Amines. XXIV. Preparation and Crystal Structures of Bis(dimesylamino)dimethyl Silane and Bis(dimesylamino)dimethyl StannaneThe new compounds (CH3)2E[N(SO2CH3)2]2 with E = Si (3), m.p. 162 °C, and E = Sn (4), m.p. 194-196 ° were prepared by metathesis of AgN(SO2CH3)2 with (CH3)2ECl2 and subjected to X-ray structure determinations. 3 crystallizes in the monoclinic space group C2/c with a = 1714.3(4), b = 679.6(2), c = 1389.9(4) pm, β = 97.50(2)° and Z = 4, 4 in the same space group with a = 2093.8(8), b = 1320.7(6), c = 1443.9(6) pm, β = 124.28(3)° and Z = 8. The crystals of both compounds consist of discrete monomeric molecules, in which the central atom E is bonded to two carbon and two nitrogen atoms in an approximately tetrahedral geometry for 3 [angles at Si in the range (105.5⃛111.9)°] and in a severely distorted tetrahedral arrangement in 4 [CSnC 128.8°; NSnN 107.8°; NSnC in the range (99.9⃛109.4)°]. Details of the molecular structures suggest that in each molecule two intramolecular E⃛O dipole-dipole interactions are stereochemically significant [Si⃛O 291.4 pm (2x); Sn⃛O 300.9 and 303.1 pm]. The molecule of 3 displays an exact, that of 4 an approximate twofold symmetry.
    Notes: Die neuen Verbindungen (CH3)2E[N(SO2CH3)2]2 mit E = Si (3), Schmp. 162 °C, und E = Sn (4), Schmp. 194-196 °C, wurden durch Metathese von AgN(SO2CH3)2 mit (CH3)2ECl2 erhalten und röntgenstrukturanalytisch charakterisiert. 3 kristallisiert in der monoklinen Raumgruppe C2/c mit a = 1714,3(4), b = 679,6(2), c = 1389,9(4) pm, β = 97,50(2)° und Z = 4, 4 in der gleichen Raumgruppe mit a = 2093,8(8), b = 1320,7(6), c = 1443,9(6) pm, β = 124,28(3)° und Z = 8. Die Kristallpackung beider Verbindungen besteht aus diskreten monomeren Molekülen, in denen das Zentralatom E an zwei Kohlenstoff- und zwei Stickstoffatome gebunden ist. 3 weist eine annähernd tetraedrische Geometrie auf [Winkel am Siim Bereich (105,5⃛111,9)°], 4 hingegen eine stark verzerrte Tetraedergeometrie [CSnC 128,8°; NSnN 107,8°; NSnC im Bereich (99,9⃛109,4)°]. Eine Betrachtung der Molekülstrukturen legt nahe, daß in beiden Fällen je zwei intramolekulare (E⃛O)-Wechselwirkungen vom Dipol-Dipol-Typ die Stereochemie beeinflussen [Si⃛O 291,4 pm (2x) Sn⃛O 300,9 und 303,1 pm]. Das Molekül von 3 besitzt eine strenge, das von 4 eine annähernde zweizählige Symmetrie.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1693-1698 
    ISSN: 0044-2313
    Keywords: Tris(trimethylsilyl)methaneselenenyl halides ; Tris(trimethylsilyl)methaneselenyl chalcogenides ; 1H, 13C, 77Se n.m.r. sprectra ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tris(trimethylsilyl)methaneselenenyl Halides and Chalcogenides.Ditrisyldiselenide (1) (trisyl = TSi = (Me3Si)3C) reacts with SOCl2, Br2 and I2 to provide trisylselenenyl halides TSiSeX (2: X = Cl; 3: X = Br, 4: X = I). Insertion of S and Se into the Se—Se bond of 1 to yield (TSiSe)2Sn (5: n = 1; 6: n = 2) and (TSiSe)2Sen (7: n = 1; 8: n = 2) was catalysed by iodine. 5 was isolated in pure state and examined by X-ray diffraction. Triselenide 7 can be cleaved by I2 in CS2 to give 4 and Se2I2 (9). From 2 with Me3SiCN and Me3SiNCS, the new selenenyl pseudohalides TSiSeCN (10) and TSiSeSCN (11) were prepared. The compounds were characterised by 1H, 13C- and 77Se n.m.r. spectra.
    Notes: Ditrisyldiselenid (1) (Trisyl  -  Tsi  -  (Me3Si)3C—) reagiert mit SOCl2, Br2 und I2 zu Trisylselenenylhalogeniden TSiSeX (2: X = Cl; 3: X = Br, 4: X = I). Die Einschiebung von Schwefel und Selen in die Se—Se-Bindung von 1 zu (TSiSe)2 Sn (5: n = 1; 6: n = 2) bzw. (TSiSe)2Sen (7: n = 1; 8: n = 2) läßt sich mit Iod katalysieren. 5 wurde in reiner Form isoliert und durch Röntgenstrukturanalyse untersucht. Das Triselenid 7 wird durch Iod in CS2 zu 4 und Se2I2 (9) gespalten. Aus 2 lassen sich mit Me3SiCN bzw. Me3SiNCS das Trisylselenocyanat TSiSeCN (10) bzw. Trisylselenenylthiocyanat TSiSeSCN (11) gewinnen. 1H, 13C- und 77Se-NMR Spektren von 1 - 11 sind im Einklang mit den Strukturvorschlägen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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