Fakultät für Chemie, Lehrstuhl für Anorganische Chemie und Strukturchemie, Universität Bielefeld, Universitätsstrasse 25, 33615, Bielefeld, Germany.
Dalton Trans. 2009 Oct 21(39):8363-9. doi: 10.1039/b911925f. Epub 2009 Aug 24.
Reactions of the lithiated carbanion [(RLi)(2).(RH)] (R = MeNCH(2)N(Me)CH, 2,4,6-trimethyl-2,4,6-triazacyclohex-1-yl) with dialkylaluminium and -gallium chlorides lead to the corresponding dialkylaluminium and -gallium compounds (RAlMe(2))(2), (RAlEt(2))(2) and (RGaEt(2))(2). They were characterised by elemental analyses, NMR spectroscopy ((1)H, (13)C, (27)Al) and crystal structure determinations. In the solid state the aluminium and gallium compounds form dimers by intermolecular coordination between the metal acceptor and the nitrogen donor leading to six-membered M(2)C(2)N(2) rings in chair conformation. As a first test for the synthetic utility of [(RLi)(2).(RH)], nucleophilic aminomethylation of chlorotrimethylsilane was performed to give RSiMe(3). Further deprotonation of RSiMe(3) with tBuLi occurs at one of the methyl groups bound to the silicon atom leading to RMe(2)SiCH(2)Li. Reactions with dimethylaluminium and -gallium chlorides gave RMe(2)SiCH(2)AlMe(2) and RMe(2)SiCH(2)GaMe(2). The compounds were characterised by NMR spectroscopy ((1)H, (13)C, (29)Si, (27)Al), elemental analyses and single crystal X-ray diffraction. The compounds are monomeric in the solid state with intramolecular M-N bonds (M = Al, Ga) leading to five-membered rings.
[(RLi)(2).(RH)]（R = MeNCH(2)N(Me)CH，2,4,6-三甲基-2,4,6-三嗪基环己-1-基）与二烷基铝和-镓氯化物的反应生成相应的二烷基铝和-镓化合物（RAlMe(2))(2)、(RAlEt(2))(2)和(RGaEt(2))(2)。它们通过元素分析、NMR 光谱（(1)H、(13)C、(27)Al）和晶体结构测定进行了表征。在固态中，铝和镓化合物通过金属受体和氮供体之间的分子间配位形成二聚体，导致椅式构象的六元 M(2)C(2)N(2)环。作为[(RLi)(2).(RH)]合成实用性的首次测试，对氯三甲基硅烷进行了亲核氨甲基化反应，得到了 RSiMe(3)。RSiMe(3)与 tBuLi 的进一步去质子化发生在与硅原子结合的一个甲基上，导致 RMe(2)SiCH(2)Li。与二甲基铝和-镓氯化物的反应得到了 RMe(2)SiCH(2)AlMe(2)和 RMe(2)SiCH(2)GaMe(2)。这些化合物通过 NMR 光谱（(1)H、(13)C、(29)Si、(27)Al）、元素分析和单晶 X 射线衍射进行了表征。这些化合物在固态中是单体的，具有分子内的 M-N 键（M = Al、Ga），导致五元环。
