31P NMR Studies Demonstrating the Assembly of catena-Phosphorus Frameworks from Chlorophosphinochlorophosphonium Cations

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• 作者：Yuen-ying Carpenter ; Neil Burford ; Michael ; D. Lumsden ; Robert McDonald
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：April 18, 2011
• 年：2011
• 卷：50
• 期：8
• 页码：3342-3353
• 全文大小：1310K
• 年卷期：v.50,no.8(April 18, 2011)
• ISSN：1520-510X

文摘

New examples of chlorophosphinochlorophosphonium (4) and chlorophosphinodichlorophosphonium (5) cations have been prepared and spectroscopically characterized. These bifunctional phosphinophosphonium cations offer a new approach to the development of phosphinophosphonium frameworks using reductive coupling reactions and have been exploited as synthons to assemble larger catena-phosphorus cations. The reactions of 4 and 5 with stibine reducing agents have been studied using ³¹P NMR spectroscopy and have been shown to produce a variety of new and known frameworks in a facile manner, depending on the reducing agent selection and the stoichiometry of the reaction. New derivatives of frameworks containing three, four, and five phosphorus atoms have been identified by ³¹P NMR spectroscopy. Crystals of the [GaCl₄]^{鈭?/sup> salt of the five-membered dication 11(iPr) have been isolated from the reaction of [4(iPr)][GaCl₄] with SbBu₃, and the solid state structural features and solution state dynamics are comprehensively described in the context of 31P{1H} NMR spectroscopic observations.}