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  • (CH3)2S derivatives  (1)
  • Tris(trimethylsilyl)methyl-derivatives, Lithium, Aluminium, Gallium, Indium  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1633-1638 
    ISSN: 0044-2313
    Keywords: (CH3)2S derivatives ; Structure ; Spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (CH3)2SBr2 - Reactions and Structures(CH3)2SBr2 (1) is a donor acceptor complex (8-S-3 + 10-Br-2) which reacts with (CH3)2S(=O)NSi(CH3)3 to yield [(CH3)2S(O)=N—S(CH3)2]+Br- (2). With SbBr3 (CH3)2SBr+SbBr4- (3) can be isolated. 1 crystallizes monoclinic in the space group P21/c with a = 733.8, b = 734.2, c = 1132.7 pm, β = 92.8° and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 967.2, b = 793.3, c = 1168.3 pm and Z = 4. The SBr and BrBr force constants of 1 are compared with those of S2Br2, 3 and Br2 resp. The nmr and mass spectra of 1 and 2 are communicated.
    Notes: (CH3)2SBr2 (1) ist ein (8-S-3 + 10-Br-2) Donor-Akzeptor-Komplex(8-S-3 + 10-Br-2) bedeutet: acht Valenzelektronen am S-Atom, das von drei Bindungspartnern umgeben ist, und zehn Valenzelektronen am Br-Atom, das zwei Bindungspartner hat; s.: S. W. Perkins, J. C. Martin, A. J. Arduengeo III, W. Lau, A. Alegria, J. K. Kochi, J. Am. Chem. Soc. 1980, 102, 7753. und reagiert mit (CH3)2S(=O)NSi(CH3)3 zu [(CH3)2S(O)=N—S(CH3)2]+Br- (2), mit SbBr3 zu (CH3)2SBr+SbBr4- (3). 1 kristallisiert monoklin (P21/c) mit a = 733,8, b = 734,2, c = 1132,7 pm, β = 92,8° und Z = 4. 2 kristallisiert orthorhombisch in der Raumgruppe Pnma mit a = 967,2, b = 793,3, c = 1168,3 pm und Z = 4. Die SBr- und BrBr-Kraftkonstanten von 1 werden mit denen von S2Br2 und 3 bzw. Br2 verglichen. Die NMR- und Massenspektren von 1 und 2 werden kurz diskutiert.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1455-1466 
    ISSN: 0044-2313
    Keywords: Tris(trimethylsilyl)methyl-derivatives, Lithium, Aluminium, Gallium, Indium ; spectra ; X-ray Structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Base-free Tris(trimethylsilyl)methyl Derivatives of Lithium, Aluminium, Gallium, and IndiumBase-free LiR* (R*=-C(SiMe3)3) has been prepared from R*Cl and Li-metal in toluene at 85-90°C and used to synthesize the metallanes R*MMe2 with M = Al, Ga and In, respectively. The NMR (1H, 13C, 29Si) and the vibrational spectra of these trisyl compounds have been discussed.AlCl3 and LiR*(ratio 1 : 1) forms the metallate metallate Li[R*AlCl3]. The triclinic unit cell (space group P1) consists of a centrosymmetric assoziate, formed by four Li[R*AlCl3]- units with Al—Cl…Li bridges, two pairs of Li-atoms differing in their chlorine-coordination and two disordered toluene molecules, inserted in the crystal lattice (R1wR2 =0,0444/0,1072).The reaction of GaCl3 with LiR* (I :1) gives the unusual sesquichloride (R*Ga(Cl1,33)Me0,67)3 in moderate yield. The X-ray structure determination shows a Ga3Cl3-skeleton with chairconformation and disordered, terminal gallium ligands (R1/wR2= 0,0646/0,2270).
    Notes: Basefreies LiR* (R*=-C(SiMe3)3) wurde aus R*Cl und Lithiummetall in Toluol bei 85-90°C erhalten und zur Darstellung der Dimethylmetallane R*MMe2 mit M = Al, Ga, In verwendet, die durch NMR- (1H, 13C, 29Si) und Schwingungsspektren (Raman, IR) charakterisiert werden.AlCl3 und LiR* (Molverhältnis 1 : 1) bilden das Metallat Li[R*AlCl3]. Die trikline Einheitszelle (Raumgruppe P1) enthält ein zentrosymmetrisches, über Al—Cl … Li—Brücken gebildetes Assoziat aus vier Li[R*AlCl3]-Einheiten, mit zwei paarweise unterschiedlich von Chlor koordinierten Li-Atomen sowie zwei fehlgeordnete Toluolmoleküle (R1/ wR2 = 0,0444/0,1072).Die Reaktion von GaCl3 mit LiR* (1 : 1) in Toluol führt in mäßiger Ausbeute zum ungewöhnlichen Sesquichlorid (R*Ga(Cl1,33)Me0,67)3. Die Röntgenstrukturanalyse zeigt ein sesselförmig gewelltes Ga3Cl3-Sechsringgerüst und fehlgeordnete, terminale Liganden am Galliumatom (R1/ wR2 = 0,0646/0,2270).Li[R*AlCl3]. The triclinic unit cell (space group P1) consists of a centrosymmetric assoziate, formed by four Li[R*AlCl3]-units with Al-Cl … Li bridges, two pairs of Li-atoms differing in their chlorine-coordination and two disordered toluene molecules, inserted in the crystal lattice (R1/wR2 = 0,0444/0,1072).The reaction of GaCl3 with LiR* (1 : 1) gives the unusual sesquichloride (R*Ga(Cl1,33)Me0,67)3 in moderate yield. The X-ray structure determination shows a Ga3Cl3-skeleton with chairconformation and disordered, terminal gallium ligands (R1/wR2 = 0,0646/0,2270).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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