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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Transmetallation and silylation products of aminal carbanions
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Transmetallation and silylation products of aminal carbanions

机译：动物碳负离子的重金属化和甲硅烷基化产品

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摘要

Reactions of the lithiated carbanion [(RLi)_2.(RH)] (R = MeN[CH_2N(Me)]_2,CH, 2,4,6-trimethyl-2,4,6-triazacyclohex-1-yl) with dialkylaluminium and -gallium chlorides lead to the correspondingdialkylaluminium and -gallium compounds (RAlMe_2)_2, (RAlEt_2)_2and (RGaEt_2)_2. They werecharacterised by elemental analyses, NMR spectroscopy (~1H,~13C,~27Al) and crystal structuredeterminations. In the solid state the aluminium and gallium compounds form dimers by intermolecularcoordination between the metal acceptor and the nitrogen donor leading to six-membered M_2C_2N_2rings in chair conformation. As a first test for the synthetic utility of [(RLi)_2.(RH)], nucleophilicaminomethylation of chlorotrimethylsilane was performed to give RSiMe_3. Further deprotonationof RSiMe_3, with tBuLi occurs at one of the methyl groups bound to the silicon atom leading toRMe_2SiCH_2Li. Reactions with dimethylaluminium and -gallium chlorides gave RMe_2SiCH_2AlMe_2andRMe_2SiCH_2GaMe_2. The compounds were characterised by NMR spectroscopy (~1H, ~13C,~29 Si,~27 Al),elemental analyses and single crystal X-ray diffraction. The compounds are monomeric in the solidstate with intramolecular M-N bonds (M = Al, Ga) leading to five-membered rings.
机译：锂化碳负离子[（RLi）_2。（RH）]（R = MeN [CH_2N（Me）] _ 2，CH，2,4,6-trimethyl-2,4,6-triazacyclohex-1-yl）的反应二烷基铝和-镓氯化物可生成相应的二烷基铝和-镓化合物（RAlMe_2）_2，（RAlEt_2）_2和（RGaEt_2）_2。它们的特征在于元素分析，NMR光谱法（〜1H，〜13C，〜27Al）和晶体结构测定。在固态下，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，从而导致椅子构象中的六元M_2C_2N_2环。作为[[RLi）_2。（RH）]的合成效用的第一个测试，进行了氯三甲基硅烷的亲核氨基甲基化，得到RSiMe_3。 RSiMe_3用tBuLi进一步去质子化发生在与硅原子键合的甲基之一上，从而导致RMe_2SiCH_2Li。与二甲基铝和氯化镓反应，得到RMe_2SiCH_2AlMe_2和RMe_2SiCH_2GaMe_2。化合物通过NMR光谱（〜1H，〜13C，〜29 Si，〜27 Al），元素分析和单晶X射线衍射进行表征。该化合物为固态的单体，具有分子内的M-N键（M = Al，Ga），形成五元环。

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