Structure and Solution Reactivity of (Triethylsilylium)triethylsilane Cations
Structure and Solution Reactivity of (Triethylsilylium)triethylsilane Cations
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DOI：
10.1021/om400970j
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发表时间：
2013-12-23
期刊：
影响因子：
2.8
通讯作者：
Heinekey, D. Michael
中科院分区：
文献类型：
--
作者：
Connelly, Samantha J.;Kaminsky, Werner;Heinekey, D. Michael
三苯基甲基四（五氟苯基）硼酸盐[Ph 3C] [B（C6 F5）（4）]与过量的纯三乙基硅烷反应，得到三乙基甲硅烷基（三乙基硅烷）四（五氟苯基）硼酸盐[（Et 3Si）（2）（μ-H）] [B（C6 F5）（4）]（1），通过X射线晶体学鉴定。在氯苯和氟苯中，在溶液中观察到1。当1溶解在苯或甲苯中时，所放出的气体显示为氢气。同位素标记实验表明，氢来自于Et 3SiH与芳烃溶剂的硅鎓络合物的反应。
Reaction of triphenylmethylium tetrakis(pentafluorophenyl)borate, [Ph3C] [B(C6F5)(4)], with excess neat triethylsilane affords triethylsilylium(triethylsilane) tetrakis(pentafluorophenyl)borate, [(Et3Si)(2)(mu-H)] [B(C6F5)(4)] (1), identified by X-ray crystallography. In chlorobenzene and fluorobenzene, 1 is observed in solution. When 1 is dissolved in benzene or toluene, the evolved gas was shown to be hydrogen. Isotope labeling experiments demonstrate that the hydrogen arises from the reaction of Et3SiH with the silylium complex of the arene solvent.