From hypervalent xenon difluoride and aryliodine(III) difluorides to onium salts: Scope and limitation of acidic fluoroorganic reagents in the synthesis of fluoroorgano xenon(II) and iodine(III) onium salts
From hypervalent xenon difluoride and aryliodine(III) difluorides to onium salts: Scope and limitation of acidic fluoroorganic reagents in the synthesis of fluoroorgano xenon(II) and iodine(III) onium salts
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DOI：
10.1016/j.jfluchem.2006.05.008
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发表时间：
2006-10-01
影响因子：
1.9
通讯作者：
Westphal, Ulrich
中科院分区：
文献类型：
--
作者：
Abo-Amer, Anwar;Frohn, Hermann-Josef;Westphal, Ulrich
氟化有机二氟硼烷RfBF 2 通常是适合将XeF 2 和RIF 2 分别转化成相应的四氟硼酸鎓盐[RfXe][BF 4 ]和[R(R-f)I][BF 4 ]的试剂。 (4-C5F4N)BF2 和反式-CF3CF=CFBF2 代表高酸度的硼烷，在与 XeF2 反应时不形成 Xe-C 鎓盐，但与 RIF2 反应生成所需的碘鎓盐 (R = C6F5, o-, m-, p-C6FH4)。 (4-C5F4N)BF2 与 XeF2 的反应以 XeF2-硼烷加合物结束。 C6F5Xe(4-C5F4N)是第一个Xe-(4-C5F4N)化合物，当C6F5XeF与Cd(4-C5F4N)(2)反应时得到。我们描述了 (4-C5F4N)IF2 的合成以及 (4-C5F4N)IF2 和 C6F5IF2 与 (4-C5F4N)BF2 的反应。类似于[(4-C5F4N)(2)I][BF4]和[C6F5(4-C5F4N)I][BF4]芳基(全氟烯基)碘鎓盐[R(R')I][BF4]由RIF2(R = C6F5、o-、m-、p-C6FH4)和R'BF2(R'=反式-CF3CF=CF)获得， CF2=CF）。计算了选定的氟有机二氟硼烷 RfBF2 及其烃类似物的气相氟化物亲和力 pF(-) (B3LYP/6-31+G*)，并讨论了它们将 R-f-基团引入超价 EF2 键的潜力。介绍了在路易斯酸性试剂 RAF(n-1) (A = B, P; n = 3, 5) 作用下影响超价 EF2 键 (E = Xe, R'I} 转化为相应的 [RE][AF(n+1)] 盐的四个方面，并强调了酸性的重要作用。氟化物亲和力可能有助于计划将有机基团引入 EF2 部分并扩大酸性试剂的类型。 C6H5PF4 的 pF(-) 值与 RfBF2 化合物相当，能够将 C6H5 基团引入 RIF2 (R = C6F5, P-C6FH4) (c) 2006 Elsevier B.V. 保留所有权利。
Fluorinated organodifluoroboranes RfBF2 are in general suitable reagents to transform XeF2 and RIF2 into the corresponding onium tetrafluoroborate salts [RfXe][BF4] and [R(R-f)I][BF4], respectively. (4-C5F4N)BF2 and trans-CF3CF=CFBF2 Which represent boranes of high acidity form no Xe-C onium salts in reactions with XeF2 but give the desired iodonium salts with RIF2 (R = C6F5, o-, m-, p-C6FH4). The reaction of (4-C5F4N)BF2 with XeF2 ends with a XeF2-borane adduct. C6F5Xe(4-C5F4N), the first Xe-(4-C5F4N) compound, was obtained when C6F5XeF was reacted with Cd(4-C5F4N)(2). We describe the synthesis of (4-C5F4N)IF2 and reactions of (4-C5F4N)IF2 and C6F5IF2 with (4-C5F4N)BF2. Analogous to [(4-C5F4N)(2)I][BF4] and [C6F5(4-C5F4N)I][BF4] aryl(perfluoroalkenyl)iodonium salts [R(R')I][BF4] were obtained from RIF2 (R = C6F5, o-, m-, p-C6FH4) and R'BF2 (R'= trans-CF3CF=CF, CF2=CF). The gas phase fluoride affinities pF(-) of selected fluoroorganodifluoroboranes RfBF2 and their hydrocarbon analogs are calculated (B3LYP/6-31+G*) and discussed with respect to their potential to introduce R-f-groups into hypervalent EF2 bonds. Four aspects which influence the transformation of hypervalent EF2 bonds (E = Xe, R'I} under the action of Lewis acidic reagents RAF(n-1) (A = B, P; n = 3, 5) into the corresponding [RE][AF(n+1)] salts are presented and the important role of the acidity is emphasized. Fluoride affinities may help to plan the introduction of organo groups into EF2 moieties and to expand the types of acidic reagents. Thus C6H5PF4 with a pF(-) value comparable to that of RfBF2 compounds is able to introduce the C6H5 group into RIF2 (R = C6F5, P-C6FH4). (c) 2006 Elsevier B.V. All rights reserved.