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Synthesis, characterization, and application of two Al(OR ~F) _3 lewis superacids

机译:两种Al(OR〜F)_3刘易斯超酸的合成,表征及应用

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We report herein the synthesis and full characterization of the donor-free Lewis superacids Al(OR F) _3 with OR F=OC(CF _3) _3 (1) and OC(C _5F _(10))C _6F _5 (2), the stabilization of 1 as adducts with the very weak Lewis bases PhF, 1,2-F _2C _6H _4, and SO _2, as well as the internal C-F activation pathway of 1 leading to Al _2(F)(OR F) _5 (4) and trimeric [FAl(OR F) _2] _3 (5, OR F=OC(CF _3) _3). Insights have been gained from NMR studies, single-crystal structure determinations, and DFT calculations. The usefulness of these Lewis acids for halide abstractions has been demonstrated by reactions with trityl chloride (NMR; crystal structures). The trityl salts allow the introduction of new, heteroleptic weakly coordinating [Cl-Al(OR F) _3] ~- anions, for example, by hydride or alkyl abstraction reactions. A super method! The synthesis of the donor-free Lewis superacids Al(OR ~F) _3 with OR ~F=OC(CF _3) _3 (1) and OC(C _5F _(10))C _6F _5 (2), as well as stabilization of 1 with the very weak Lewis bases PhF, 1,2-F _2C _6H _4, and SO _2, is reported (see figure). Applications of 1 and 2 in bond heterolysis reactions with Cl-CPh _3 giving the trityl cation and the respective weakly coordinating anion [ClAl(OR ~F) _3] ~- are also described.
机译:我们在此报告了无供体的路易斯超酸Al(OR F)_3与OR F = OC(CF _3)_3(1)和OC(C _5F _(10))C _6F _5(2)的合成和完整表征,具有极弱路易斯碱PhF,1,2-F _2C _6H _4和SO _2的1作为加合物的稳定化,以及1导致Al _2(F)(OR F)_5的内部CF活化途径(4)和三聚体[FA1(OR F)_2] _3(5,或F = OC(CF _3)_3)。从NMR研究,单晶结构测定和DFT计算中获得了见识。通过与三苯甲基氯的反应(NMR;晶体结构)证明了这些路易斯酸对卤化物提取的有用性。三苯甲基盐允许例如通过氢化物或烷基提取反应引入新的杂配弱配位的[Cl-Al(OR F)_3]-阴离子。超级方法!具有OR〜F = OC(CF _3)_3(1)和OC(C _5F _(10))C _6F _5(2)的无给体路易斯超酸Al(OR〜F)_3的合成以及据报道,极弱的路易斯碱PhF,1,2-F _2C _6H _4和SO _2使1稳定(见图)。还描述了1和2在与Cl-CPh _3产生三苯甲基阳离子和相应的弱配位阴离子[ClAl(OR〜F)_3]〜-的键杂解反应中的应用。

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