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  • 1
    ISSN: 0009-2940
    Schlagwort(e): Spirosilicates, zwitterionic ; Silicon, pentacoordinate ; Bond cleavage, Si - C ; Solid-state NMR, 29Si and 15N ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: New Zwitterionic λ51-Spirosilicates: Syntheses, Single-Crystal X-Ray Structure Analyses, and Solid-State NMR StudiesThe zwitterionic spirocyclic λ51-silicates bis[3,4,5,6-tetrabromo-1,2-benzenediolato(2-)][2-(pyrrolidinio)ethyl]silicate (5; and its monohydrate 5 · H2O) and bis[1,2-benzenediolato(2-)]1-[(dimethylammonio)methyl]silicate (6) were synthesized by various methods including Si - C bond cleavage reactions. The crystal structures of 5, 5·H2O, and 6 were investigated by X-ray diffarction. Furthermore, 5, 5·H2O, 6, and the related zwitterionic λ51-spirosilicates 1·1/4 CH3CN, 2·CH3CN, 3·CH3CN, and 4 were characterized by solid-state NMR spectroscopy (29Si and 15N CP/MAS). The pentacoordinate silicon atoms of 5, 5·H2O (two cystallographically independent zwitterions and two crystallographically independent water molecules), and 6 (two crystallographically independent zwitterions) are surrounded by four oxygen atoms and one carbon atom. The coordination polyhedrons around the silicon atoms of 5 and 6 can be described as distorted (5) or nearly ideal (6) trigonal bipyramids, the carbon atoms being in equatorial positions. 5 forms intramolecular and 6 intermolecular (→ for-mation of dimeric units) N - H…O hydrogen bonds. The co-ordination polyhedrons around the two crystallographically independent silicon atoms of 5·H2O can be described as a nearly ideal and slightly distorted square pyramid, respectively, the carbon atoms being in the apical positions. In the crystal lattice of 5·H2O, intermolecular N - H…O O - H…O hydrogen bonds between the zwitterions and water molecules are observed. The results obtained by X-ray diffraction and solid-state NMR spectroscopy are consistent for each compound studied.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 2
    ISSN: 0009-2940
    Schlagwort(e): Germane, optically active ; Biotransformation, stereoselective ; Transesterification, enzymatic ; Porcine liver esterase ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthesis of ( - )-(Acetoxymethyl)(hydroxymethyl)methyl(phenyl)germane [( - )-MePhGe(CH2OAc)(CH2OH)] by an Esterase-Catalyzed Transesterification: the First Enzymatic Synthesis of an Optically Active GermaneThe prochiral germane MePhGe(CH2OH)2 (1) was synthesized by a six-step synthesis starting from GeCl4 (3) [3 → Cl2Ge(CH2Cl)2 (4) → Ph2Ge(CH2Cl)2 (5) → (CF3S(O)2O)PhGe(CH2Cl)2 (6) → MePhGe(CH2Cl)2 (7) → MePhGe(CH2OAc)2 (8) → 1]. Reaction of 1 with Ac2O/NEt3 (molar ratio 1: Ac2O = 1:1) gave the racemic germane rac-MePhGe(CH2OAc)(CH2OH) (rac-2). Stereoselective transesterification of 1 with vinyl acetate (acetate source and solvent), catalyzed by immobilized porcine liver esterase (PLE; E.C.-3.1.1.1), yielded the optically active germane ( - )-MePhGe(CH2OAc)(CH2OH) [( - )-2] (yield 57%, enantiomeric purity 50% ee).
    Materialart: Digitale Medien
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 643-646 
    ISSN: 0009-2940
    Schlagwort(e): λ5-Germanate, zwitterionic ; Germanium, pentacoordinate ; Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The zwitterionic spirocyclic λ5-germanate bis[2,3-naphthalenediolato(2 - )](pyrrolidiniomethyl)germanate (8) was synthesized and the crystal structure of its tetartoacetonitrile solvate 8 · 1/4 CH3CN studied by single-crystal X-ray diffraction. Compound 8 was prepared by reaction of (MeO)3-GeCH2NC4H8 (11; NC4H8 = pyrrolidino) with two equivalents of 2,3-naphthalenediol (isolated as 8 · 1/4 CH3CN; yield 92%). The coordination polyhedron around the pentacoordinate germanium atom of 8 · 1/4 CH3CN can be described as a strongly distorted trigonal bipyramid (the structure is displaced by 38.9% from the ideal trigonal bipyramid towards the ideal square pyramid), the carbon atom occupying an equatorial position. In the crystal lattice of 8 · 1/4 CH3CN, the zwitterions form intermolecular N—H⃛O hydrogen bonds leading to the formation of dimers. 1H- and 13C—NMR studies revealed that 8 also exists in solution ([D6]DMSO).
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Standort Signatur Einschränkungen Verfügbarkeit
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