Selective anion encapsulation by a metalated cryptophane with a pi-acidic interior.
Selective anion encapsulation by a metalated cryptophane with a pi-acidic interior.
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通过具有π酸性内部的金属化隐花烷选择性封装阴离子。
DOI：
10.1021/ja055560i
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发表时间：
2005
影响因子：
15
通讯作者：
K. Travis Holman
中科院分区：
文献类型：
--
作者：
Robert M. Fairchild;K. Travis Holman
分子胶囊(+/-)-隐烷- e的外芳烃面与[Cp*Ru]+基团的金属化产生了一个能够包封阴离子的pi酸性腔。对[CF3SO3]-和[SbF6]-盐进行了晶体学表征，并证明了这些阴离子被金属化隐烷包裹。1H和19F NMR谱建立了NO2CD3溶液中阴离子的结合，揭示了腔体对不同阴离子（KX-/KOTf-）的相对亲和力：[BF4]-近似为0，[PF6]- = 1.18， [CF3SO3]-与1相同，[SbF6]- = 0.30。变温速率研究表明，三氟酸盐包封的激活屏障为DeltaG298K = 18.0(8) kcal.mol-1 (DeltaH = 17.5（4) kcal.mol-1和DeltaS = 2(1) cal.mol-1 - k -1）。
Metalation of the exterior arene faces of the molecular capsule (+/-)-cryptophane-E with [Cp*Ru]+ moieties results in a pi-acidic cavity capable of encapsulating anions. The [CF3SO3]- and [SbF6]- salts have been crystallographically characterized and demonstrate the encapsulation of these anions by the metalated cryptophane. 1H and 19F NMR spectroscopy establish the binding of anions in NO2CD3 solution and reveal the relative affinity of the cavity for different anions (KX-/KOTf-): [BF4]- approximately 0, [PF6]- = 1.18, [CF3SO3]- identical with 1, [SbF6]- = 0.30. Variable temperature rate studies reveal the activation barrier for triflate encapsulation to be DeltaG298K = 18.0(8) kcal.mol-1 (DeltaH = 17.5(4) kcal.mol-1 and DeltaS = 2(1) cal.mol-1.K-1).