Dehydrogenation of LGeH by a Lewis N-Heterocyclic Carbene Borane Pair under the Formation of L′Ge and its Reactions with B(C6F5)3 and Trimethylsilyl Diazo

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• 作者：Anukul Jana ; Ina Objartel ; Herbert W. Roesky ; Dietmar Stalke
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：August 17, 2009
• 年：2009
• 卷：48
• 期：16
• 页码：7645-7649
• 全文大小：758K
• 年卷期：v.48,no.16(August 17, 2009)
• ISSN：1520-510X

文摘

Herein we report the dehydrogenation of LGeH (1) [L = CH{(CMe)(2,6-iPr₂C₆H₃N)}₂] by a frustrated Lewis NHC borane pair under the formation of an imidazolium borate salt (2) and the heterocyclic germylene L′Ge (3) [L′ = CH{(C═CH₂)(CMe)(2,6-iPr₂C₆H₃N)₂}]. The reaction of 3 with B(C₆F₅)₃ in toluene results in the formation of a zwitterion containing a germylene moiety, [B(C₆F₅)₃L′′Ge] (4) [L′′ = CH{(CCH₂)(CMe)(2,6-iPr₂C₆H₃N)₂}]. Subsequent treatment of 4 with 1 equiv of 1,3-di-tert-butylimidazol-2-ylidene (NHC) gives B(C₆F₅)₃L′′′Ge (5) [L′′′ = CH{(C═CH₂)(CCH₂B(C₆F₅)₃)(2,6-iPr₂C₆H₃N)₂}] under formation of the imidazolium cation. Moreover compound 3 reacts with trimethylsilyl diazomethane (N₂CHSiMe₃) to form the diazogermylene LGeC(N₂)SiMe₃ (6) under C−H bond cleavage. Compound 6 slowly rearranges to the isonitriletrimethylsilyl germanium(II) amide LGeN(SiMe₃)NC (6a). All compounds were characterized by microanalysis and multinuclear NMR spectroscopy. Compounds 4, 6, and 6a were unequivocally identified by single crystal X-ray structure analysis.