Synthesis of Silylium and Germylium Ions by a Substituent Exchange Reaction
Synthesis of Silylium and Germylium Ions by a Substituent Exchange Reaction
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DOI：
10.1021/om400366z
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发表时间：
2013-09-09
期刊：
影响因子：
2.8
通讯作者：
Mueller, Thomas
中科院分区：
文献类型：
--
作者：
Schaefer, Andre;Reissmann, Matti;Mueller, Thomas
研究了二芳基烷基硅烷和锗烷在弱配位的E阴离子存在下与三苯甲基阳离子反应生成相应的三芳基硅鎓或锗烷H离子。研究了促进取代基交换的因素，发现取代基、溶剂和44族元素对取代基交换有显著影响。三（五甲基苯基）硅鎓硼酸盐[（Me_5C_6）（3）Si]（2）[B_（12）Cl_（12）]的固态XRD和NMR研究揭示了硅鎓离子中硅原子的三角平面配位环境。NMR研究表明，2，4，6-三异丙基苯基取代的硅鎓和锗鎓离子在异丙基的CH键与带正电荷的14族元素原子之间发生C-H中心点E+三中心相互作用（E = Si，Ge）.
The reaction of diarylalkylsilanes and -germanes with trityl cation in the presence of a weakly coordinating E anion to give the corresponding triarylsilylium or -germylium H ions was investigated. This reaction provides a facile access to a factors, that promote the substituent exchange were studied, and significant effects of the substitUent, of the solvent, and of the group 44 element were revealed. A combined solid-state XRD and NMR investigation of the tris(pentamethylphenyl) silylium borate [(Me5C6)(3)Si](2)[B12Cl12] disclosed the trigonal.planar coordination environment of the silicon atom in this silylium ion. NMR investigations indicate for 2,4,6-triisopropylphenylsubstituted silylium and germylium ions the onset of C-H center dot center dot center dot E+ three-center interactions (E = Si, Ge) between the distant CH bond of the isopropyl group and the positively charged group 14 element atom.