29Si NMR observation of an unprecedented rearrangement in tetraaryldisilenes
29Si NMR observation of an unprecedented rearrangement in tetraaryldisilenes
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29Si NMR 观察到四芳基二硅烯中前所未有的重排
DOI：
10.1021/ja00274a074
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发表时间：
1986
影响因子：
15
通讯作者：
R. West
中科院分区：
文献类型：
--
作者：
H. Yokelson;J. Maxka;D. Siegel;R. West
作者在这里报告的第一个观察到的一个简单的分子内重排tetraaryldisilenes涉及交换的硅-硅双键的硅原子之间的两个芳基取代基。在-60/sup 0/C下，通过辐照其三硅烷前体在戊烷溶液中的光化学反应生成二硅烯，并在苯中用1 sup 29/Si NMR检测了粗光解产物。两个纯的二硅烯产生的三硅烷的光解，并在每种情况下，只有一个单一的/sup 29/Si信号在二硅烯区域，分别在63.68和64.06 ppm。当照射两种三硅烷的等摩尔混合物时，最初在二硅烯区域（60-65 ppm）中以约1：1：1：1的强度比观察到四个信号。这些结果与现在已经确立的亚甲硅烷基在溶液中二聚得到二硅烯的结果一致。
The authors report here the first observation of a facile intramolecular rearrangement of tetraaryldisilenes involving the exchange of two aryl substituents between the silicon atoms of the silicon-silicon double bond. The disilenes were generated photochemically by irradiation of their trisilane precursors in pentane solution at -60/sup 0/C and the crude photolysates were examined by /sup 29/Si NMR in benzene. Two pure disilenes were produced by photolysis of trisilanes and gave in each case only a single /sup 29/Si signal in the disilene region, at 63.68 and 64.06 ppm, respectively. When an equimolar mixture of the two trisilanes was irradiated, four signals were initially observed in the disilene region (60-65 ppm) in an approximately 1:1:1:1 intensity ratio. These results are consistent with the now well-established dimerization of silylenes in solution to give disilenes.