Intramolecular Lewis acid-base pairs based on 4-ethynyl-2,6-lutidine.

Intramolecular Lewis acid-base pairs based on 4-ethynyl-2,6-lutidine.
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基于 4-乙炔基-2,6-二甲基吡啶的分子内路易斯酸碱对

DOI:
10.1039/c2dt30719g
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发表时间:
2012
影响因子:
4
通讯作者:
N. W. Mitzel
N. W. Mitzel
中科院分区:
化学2区
文献类型:
--
作者:
D. Winkelhaus;B. Neumann;H.-G. Stammler;N. W. Mitzel

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4-乙炔基-2,6-二甲基吡啶(2,6-Me 2)(4-HCC)C5 H2 N(2)与B(C6 F5)3反应,经去质子化途径得到两性吡啶[(2,6-Me 2)(4-(C6 F5)3BCC)C5 H2 NH](3)。通过用第13族三烷基AlMe 3、AlEt 3、GaMe 3、GaEt 3和InMe 3处理2,在相应烷烃的挤出下,乙炔基的金属化得到化合物4-8。所得产物通过元素分析和NMR光谱表征。化合物4和8从THF中结晶并作为具有配位THF分子的单体产生。镓化合物7可以从苯中结晶出来,得到配位聚合物。通过单晶X-射线衍射实验确定了这三个化合物(4·THF、7和8·2 THF)的结构。铝化合物4和5表现出取代基的再分配反应。
The reaction of 4-ethynyl-2,6-lutidine, (2,6-Me2)(4-HCC)C5H2N (2), with B(C6F5)3 afforded the zwitterion [(2,6-Me2)(4-(C6F5)3BCC)C5H2NH] (3) via a deprotonation pathway. By treatment of 2 with the group 13 trialkyls AlMe3, AlEt3, GaMe3, GaEt3 and InMe3, metallation of the ethynyl group afforded compounds 4–8 under extrusion of the corresponding alkane. The resulting products were characterised by elemental analyses and NMR spectroscopy. Compounds 4 and 8 were crystallized from THF and were yielded as monomers with coordinated THF molecules. The gallium compound 7 could be crystallised from benzene and was afforded as coordination polymer. The structures of these three compounds (4·THF, 7 and 8·2THF) were determined by single-crystal X-ray diffraction experiments. The aluminium compounds 4 and 5 show redistribution reaction of their substituents.
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