STABLE SOLID SILAETHYLENES
STABLE SOLID SILAETHYLENES
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DOI：
10.1021/ja00385a019
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发表时间：
1982-01-01
影响因子：
15
通讯作者：
WONGNG, W
中科院分区：
文献类型：
--
作者：
BROOK, AG;NYBURG, SC;WONGNG, W
从同分异构体酰基硅烷的光解中分离出固体硅乙烯，即1，1-双（三甲基硅烷基）-2-（三甲基硅氧基）-2-（1-金刚烷基）-1-硅乙烯（2c）。用IR、拉曼、UV、~ 1H NMR、~（13）C NMR、~（29）Si NMR、质谱和电离势对产物进行了表征。晶体结构显示出轻微扭曲的分子，硅碳双键长度为1.764 π。该分子在空气中剧烈冒烟，生成环状三硅氧烷和金刚烷-1-羧酸的甲硅烷基酯。其他反应和比较与其他硅乙烯在溶液中进行了说明。1967年，Gusel'nikov和Flowers首次提出有力的证据，证明硅烯（silene）可能存在，但只是作为过渡中间体存在。随后的密集研究活动2产生了一个挑战，看看硅乙烯是否可以在室温下充分稳定存在一段时间。我们已经解决了这一挑战，现在报告的分离和表征的两个固体硅乙烯，无限期稳定在室温下氩气。3我们先前已经证实4，几种三（三甲基甲硅烷基）酰基硅烷（1）干净地进行光化学重排
A solid silaethylene, 1, 1-bis (trimethylsilyl)-2-(trimethylsiloxy)-2-(1-adamantyl)-1-silaethene (2c), has been isolated from the photolysis of the isomeric acylsilane. The silaethylene was characterized by IR, Raman, UV,* H NMR, 13C NMR, 29Si NMR, and mass spectroscopy and by its ionization potential. The crystal structure shows a slightly twisted molecule with a silicon-carbon double-bond length of 1.764 Á. The molecule smokes vigorously in air, yielding a cyclic trisiloxane and the silyl ester of adamantane-1-carboxylic acid. Other reactions and comparisons with other silaethylenes in solution are described. In addition, 1, 1-bis (trimethylsilyl)-2-(trimethylsiloxy)-2-(1, 1-diethylpropy 1)-1-silaethene (2b) has been obtained as a solid.Research on silaethylenes (silenes) has growndramatically since 1967, when Gusel’nikov andFlowers1 presented compelling evidence for the first time that these species could exist, if only as transient intermediates. The subsequent intense research activity2 generated the challenge to see whether a silaethylene could be sufficiently stabilized to exist for some time at room temperature. We have addressed this challenge and now report the isolation and characterization of two solid silaethylenes, indefinitely stable at room temperature under argon. 3 We have previously reported4 that several tris (trimethyl-silyl) acylsilanes (1) cleanly undergo photochemical rearrangement