Jana Anukul, Objartel Ina, Roesky Herbert W, Stalke Dietmar
Institut für Anorganische Chemie, Universität Göttingen, Germany.
Inorg Chem. 2009 Aug 17;48(16):7645-9. doi: 10.1021/ic900341r.
Herein we report the dehydrogenation of LGeH (1) [L = CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(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 horizontal lineCH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}]. The reaction of 3 with B(C(6)F(5))(3) in toluene results in the formation of a zwitterion containing a germylene moiety, [B(C(6)F(5))(3)L''Ge] (4) [L'' = CH{(CCH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}]. Subsequent treatment of 4 with 1 equiv of 1,3-di-tert-butylimidazol-2-ylidene (NHC) gives B(C(6)F(5))(3)L'''Ge (5) [L''' = CH{(C horizontal lineCH(2))(CCH(2)B(C(6)F(5))(3))(2,6-iPr(2)C(6)H(3)N)(2)}] under formation of the imidazolium cation. Moreover compound 3 reacts with trimethylsilyl diazomethane (N(2)CHSiMe(3)) to form the diazogermylene LGeC(N(2))SiMe(3) (6) under C-H bond cleavage. Compound 6 slowly rearranges to the isonitriletrimethylsilyl germanium(II) amide LGeN(SiMe(3))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.
在此，我们报道了在形成咪唑鎓硼酸盐（2）和杂环亚锗烯L'Ge（3）[L' = CH{(C≡CH₂)(CMe)(2,6-iPr₂C₆H₃N)(2)}]的条件下，受阻路易斯NHC硼烷对使LGeH（1）[L = CH{(CMe)(2,6-iPr₂C₆H₃N)(2)}]脱氢。3与B(C₆F₅)₃在甲苯中反应生成含亚锗烯部分的两性离子[B(C₆F₅)₃L''Ge]（4）[L'' = CH{(C≡CH₂)(CMe)(2,6-iPr₂C₆H₃N)(2)}]。随后用1当量的1,3 -二叔丁基咪唑 - 2 - 亚基（NHC）处理4，得到B(C₆F₅)₃L'''Ge（5）[L''' = CH{(C≡CH₂)(C≡CH₂B(C₆F₅)₃)(2,6-iPr₂C₆H₃N)(2)}]，同时形成咪唑鎓阳离子。此外，化合物3与三甲基硅基重氮甲烷（N₂CHSiMe₃）反应，在C - H键断裂的情况下形成重氮亚锗烯LGeC(N₂)SiMe₃（6）。化合物6缓慢重排为异腈三甲基硅基锗（II）酰胺LGeN(SiMe₃)NC（6a）。所有化合物均通过微量分析和多核NMR光谱进行了表征。化合物4、6和6a通过单晶X射线结构分析得到了明确鉴定。
