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  • Lithium  (2)
  • Barium-bis[N,N′-bis(trimethylsilyl)benzamidinate]  (1)
  • 1
    ISSN: 1434-1948
    Keywords: Hydrogen bonds ; Indium ; Lithium ; Nitrogen heterocycles ; Zinc ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The lithiation of 2,5-di(tert-butyl)pyrrole (1) yields bis(tetrahydrofuran)lithium 2,5-di(tert-butyl)pyrrolide (2), which is monomeric in solution as well as in the solid state. Due to the coordination number of three for the lithium atom, short Li-O and Li-N bond lengths of 193 pm are observed. The metathesis reaction of 2 with tris(trimethylsilyl)-methylzinc chloride (3) gives colorless bis[tris(trimethyl-silyl)methylzinc] chloride 2,5-di(tert-butyl)pyrrolide (4). The pyrrolide ligand and the chlorine atom bridge the zinc atoms. One of the zinc atoms is bonded to the nitrogen atom of the pyrrolide substituent, while the other bonds to the opposite C-C bond. At 215 pm, the Zn-N bond is very long compared to those in alkylzinc amides, whereas the Zn-C distances lie in the range of Zn-C bond lengths found between zinc and η5-bonded cyclopentadienide ligands. The molecular structures of 1 and of the low-melting THF adduct 1·thf show a similar 2,5-di(tert-butyl)pyrrole molecule, but in the latter case a weak N-H···O bond is observed (N-H 97 pm, O···H 199 pm).
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  • 2
    ISSN: 0044-2313
    Keywords: Benzamidinates ; Strontium-bis[N,N′-bis(trimethylsilyl)benzamidinate] ; Barium-bis[N,N′-bis(trimethylsilyl)benzamidinate] ; X-ray Structures ; Spectroscopic Data ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Strontium and Barium Bis[N,N′-bis(trimethylsilyl)benzamidinates] from the Addition Reaction of the Alkaline Earth Metal Bis[bis(trimethylsilyl)amides] and BenzonitrileThe reaction of strontium bis[bis trimethylsilyl)amide] with benzonitrile yields strontium bis[N,N′- bis(trimethylsilyl)benzamidinate] · 2THF, which crystallizes in the orthorhombic space group Pbcn (a = 1845.4(3); b = 131 1,3(2); c = 1838,(3) pm; Z = 4). During the similar reaction of barium bis[bis(trimethylsilyl)amide] with benzonitrile the benzonitrile adduct barium bis[N,N′-bis(trimethylsilyl)benzamidinate] · 2 THF · benzonitrile is formed. After the addition of diphenylacetylene to the strontium di(benzamidinate) in diglyme a clathrate of the composition strontium bis[N,N′-bis(trimethylsilyl)benzamidinate] · diglyme · diphenylacetylene could be isolated; the spectroscopic data as well as the X-ray structure (monoclinic, C2/c, a = 1492.2(2); b = 1539.1(2); c = 2337.8(3)pm; Z = 4) confirm the isolated appearance of the acetylene molecule without interaction to the metal center in solution and in the solid state, respectively.
    Notes: Bei der Umsetzung des Strontiumbis[bis(trimethylsilyl)amids] mit Benzonitril in THF bildet sich Stronitium-bis[N,N′-bis(trimethylsilyl)benzamidinat] · 2THF, das in der orthorhombischen Raumgruppe Pbcn mit {a = 1 845,4(3); b = 1311,4(2); c = 1838,8(3) pm, Z = 4} kristallisiert. Die entsprechende Reaktion des Barium-bis[bis(trimethylsilyl)amids] mit Benzonitril ergibt das Benzonitril-Addukt Barium bis[N,N′ -bis(trimethylsilyl)benzamidinat] · 2 THF · Benzonitril. Nach der versuchsweisen Umsetzung des Strontium-di(benzamidinats) mit Diphenylacetylen in Diglyme läßt sich ein Clathrat der Zusammensetzung Strontiumbis[N,N′-bis(trimethylsilyl)benzamidinat] · Diglyme · Diphenylacetylen erhalten, dessen spektroskopische und strukturanalytische Untersuchungen (monoklin, C2/c, a = 1492,2(2); b = 1539,1(2); c = 2337,8(3) pm; β = 100,74(1)°; Z = 4) das Vorliegen eines unkomplexierten Diphenylacetylen-Moleküls sowohl in Lösung als auch im Festkörper bestätigen.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0009-2940
    Keywords: Lithium ; Zine ; Dibenzylzinc ; Tmeda complexes ; Heteroleptic alkylzinc amide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of lithium phenyl(trimethylsilyl)methanide with phenyl(trimethylsilyl)methylzinc chloride-tmeda in the presence of tmeda yields the addition product, a bis(tmeda)-lithium dialkylchlorozincate. The elimination of lithium chloride leads to the formation of a tmeda adduct of bis[phenyl-(trimethylsilyl)methyl]zinc. The metathesis reaction of phenyl(trimethylsilyl)methylzinc chloride-tmeda with lithium tris(trimethylsilyl)silylamide allows the isolation of the corresponding heteroleptic tmeda complex of an alkylzinc amide. The metalation of phenyl(trimethylstannyl)methane with butyllithium yields the transmetalation product benzyllithium. From the metathesis reaction of this lithium base with anhydrous zinc(II) chloride in the presence of tmeda, the tmeda adduct of dibenzylzinc crystallizes. The molecular structures of (tmeda)Li—CH(GeMe3)Ph, (tmeda)Zn(CH2Ph)2, (tmeda)Zn[CH(SiMe3)Ph]2, and (tmeda)Zn[CH(SiMe3)-Ph[N(H)Si(SiMe3)3 are reported. Whereas lithium bonds in an η3-fashion, the zinc atom forms a σ(Zn—C) bond. The extremely wide Zn—N—Si angle in (tmeda)Zn[CH(SiMe3)-Ph[N(H)Si(SiMe3)3 of 157° is remarkable.
    Additional Material: 4 Ill.
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