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• 作者：Karsten Koppe ; Vural Bilir ; Hermann-J. Frohn ; Hé ; lè ; ne P. A. Mercier ; Gary J. Schrobilgen
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：October 29, 2007
• 年：2007
• 卷：46
• 期：22
• 页码：9425 - 9437
• 全文大小：260K
• 年卷期：v.46,no.22(October 29, 2007)
• ISSN：1520-510X

文摘

New examples of [C₆F₅Xe]⁺ salts of the weakly coordinating anions [B(CF₃)₄]^-, [B(C₆F₅)₄]^-, [B(CN)₄]^-, and[B(OTeF₅)₄]^- have been synthesized by metathesis reactions of [C₆F₅Xe][BF₄] with the corresponding M^I[BY₄]salts (M^I = K or Cs; Y = CF₃, C₆F₅, CN, or OTeF₅). The salts were characterized in solution by multi-NMRspectroscopy. Their stabilities in prototypic solvents (CH₃CN and CH₂Cl₂) and decomposition products are reported.The influence of the coordinating nature of [BY₄]^- on the decomposition rate of [C₆F₅Xe]⁺ as well as the presenceof the weakly nucleophilic [BF₄]^- ion has been studied. The electrophilic pentafluorophenylation of C₆H₅F by[C₆F₅Xe][BY₄] in solvents of different coordinating abilities (CH₃CN and CH₂Cl₂) and the effects of stronger nucleophiles(fluoride and water) on the pentafluorophenylation process have been investigated. Simulations of the ¹⁹F and¹²⁹Xe NMR spectra of [C₆F₅Xe]⁺ have provided the complete set of aryl ¹⁹F-¹⁹F and ¹²⁹Xe-¹⁹F coupling constantsand their relative signs. The ¹⁹F NMR parameters of the [C₆F₅Xe]⁺ cation in the present series of salts are shownto reflect the relative degrees of cation-solvent interactions.