Ott Holger, Matthes Christoph, Ringe Arne, Magull Jörg, Stalke Dietmar, Klingebiel Uwe
Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany.
Chemistry. 2009;15(18):4602-9. doi: 10.1002/chem.200802669.
Borenes and boranes: Silylaminoiminoborenes, such as depicted, were isolated after treatment of halogen triels with silylaminofluoroboranes. In addition, novel aryl- and silyl-substituted diaminofluoroboranes were also prepared in order to substantiate this reaction route.Reactions between the halogen triels AlClMe(2), AlBr(3), GaCl(3) and the silylaminofluoroboranes (Me(3)Si)(2)NB(F)NRSiMe(3) (R=SiMe(3), CMe(3)) afforded the silylaminoiminoborenes, which were isolated as the triel adducts, such as Me(3)Si(Cl(3)Ga)NBNRSiMe(3) (6). In order to extent this reaction path to other fluoroboranes, novel aryl- and silyl-substituted diaminofluoroboranes were synthesised. Because almost no open-chain diaminofluoroboranes had been structurally characterised previously, corresponding fluoroboranes containing no silyl groups were crystallised for purposes of comparison. In complex reactions with the arylsilylaminofluoroboranes [(2,6-(iPr)(2)C(6)H(3))(Me(3)Si)NB(F)NR(2), R=iPr, iBu], amine adducts of borenium salts such as (iPr)(2)NH-->B(Bu)NH-2,6-(iPr)(2)C(6)H(3)AlCl(4) (-) (13) were obtained.
如图所示的甲硅烷基氨基亚氨基硼烯是在用甲硅烷基氨基氟硼烷处理卤化三价元素后分离得到的。此外，还制备了新型的芳基和甲硅烷基取代的二氨基氟硼烷，以证实这条反应路线。卤化三价元素AlClMe₂、AlBr₃、GaCl₃与甲硅烷基氨基氟硼烷（Me₃Si）₂NB（F）NRSiMe₃（R = SiMe₃、CMe₃）之间的反应生成了甲硅烷基氨基亚氨基硼烯，它们以三价元素加合物的形式被分离出来，如Me₃Si（Cl₃Ga）NBNRSiMe₃（6）。为了将这条反应路径扩展到其他氟硼烷，合成了新型的芳基和甲硅烷基取代的二氨基氟硼烷。由于此前几乎没有对开链二氨基氟硼烷进行过结构表征，因此制备了不含甲硅烷基的相应氟硼烷用于比较。在与芳基甲硅烷基氨基氟硼烷[（2,6 - （iPr）₂C₆H₃）（Me₃Si）NB（F）NR₂，R = iPr、iBu]的复杂反应中，得到了硼鎓盐的胺加合物，如[（iPr）₂NH→B（Bu）NH - 2,6 - （iPr）₂C₆H₃]⁺AlCl₄⁻（13）。
