Synthesis, Structural Characterization, and Reactivity Studies of 5-CF3SO3-B10H13

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• 作者：Emily R. Berkeley ; William C. Ewing ; Patrick J. Carroll ; Larry G. Sneddon
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：May 19, 2014
• 年：2014
• 卷：53
• 期：10
• 页码：5348-5358
• 全文大小：612K
• 年卷期：v.53,no.10(May 19, 2014)
• ISSN：1520-510X

文摘

In contrast to previous reactions carried out in cyclopentane solvent at room temperature that produced 6-TfO-B₁₀H₁₃ (TfO = CF₃SO₃), the reaction of closo-B₁₀H₁₀^{2鈥?/sup> with a large excess of trifluoromethanesulfonic acid in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (bmimOTf) gave exclusively the previously unknown 5-TfO-B₁₀H₁₃ isomer. Experimental and computational studies demonstrated that the difference in the products of the two reactions is a result of 6-TfO-B₁₀H₁₃ isomerizing to 5-TfO-B₁₀H₁₃ above room temperature in bmimOTf solutions. Reactivity studies showed that 5-TfO-B₁₀H₁₃: (1) is deprotonated by reaction with 1,8-bis(dimethylamino)naphthalene to form the 5-TfO-B₁₀H₁₂1鈥?/sup> anion; (2) reacts with alcohols to produce 6-RO-B₁₀H₁₃ boryl ethers (R = Me and 4-CH₃O-C₆H₄); (3) undergoes olefin-hydroboration reactions to form 5-TfO-6,9-R₂-B₁₀H₁₁ derivatives; and (4) forms a 5-TfO-6,9-(Me₂S)₂-B₁₀H₁₁ adduct at its Lewis acidic 6,9-borons upon reaction with dimethylsulfide. The 5-TfO-6,9-(Me₂S)₂-B₁₀H₁₁ adduct was also found to undergo alkyne-insertion reactions to form a range of previously unreported triflate-substituted 4-TfO-ortho-carboranes (1-R-4-TfO-1,2-C₂B₁₀H₁₀) and reactions with triethylamine or ammonia to form the first TfO-substituted decaborate [R₃NH+]₂[2-TfO-B₁₀H₉2鈥?/sup>], and [R₃NH+]₂[1-TfO-B₁₀H₉2鈥?/sup>] (R = H, Et) salts.}