Observation of Room Temperature B鈥揅l Activation of the HCB11Cl11鈥?/sup> Anion and Isolation of a Stable Anionic Carboranyl Phosphazide

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• 作者：Allen L. Chan ; Javier Fajardo ; Jr. ; James H. Wright ; II ; Matthew Asay ; Vincent Lavallo
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：November 4, 2013
• 年：2013
• 卷：52
• 期：21
• 页码：12308-12310
• 全文大小：187K
• 年卷期：v.52,no.21(November 4, 2013)
• ISSN：1520-510X

文摘

The perchlorinated carba-closo-dodecaborate anion is typically inert toward B鈥揅l functionalization. We present here the observation of two competing reactions that occur with this anion at ambient temperature. When this molecule is treated with n-BuLi and subsequently reacted with tosyl azide, a cycloaddition occurs and results in chloride substitution at a B鈥揅l vertex. The competing and dominant pathway is a substitution reaction to form the azide N₃CB₁₁Cl₁₁^{鈥?/sup>. This rare anionic carboranyl azide reacts with PPh₃ in FC₆H₅ to afford a stable anionic phosphazide. When dissolved in tetrahydrofuran, the phosphazide is in equilibrium with free PPh₃ and N₃CB₁₁Cl₁₁鈥?/sup>. Both the triazole and phosphazide are characterized by single-crystal X-ray diffraction, NMR and IR spectroscopy, and high-resolution mass spectrometry.}