The synthetic protocols, structural aspects, and spectroscopic aspects of mononuclear pseudostannatranes possessing a [4.4.3.0^1,5]tridecane cage have been reported. A tripodal ligand N(CH₂CH₂OH){CH₂(2-t-Bu-4-Me-C₆H₂OH)}₂ (H₃L) having unsymmetrical arms was reacted with n-butyltrichlorostannane, phenyltrichlorostannane, and tin tetrachloride under different solvent systems to obtain pseudostannatranes (1–3). The reaction of n-butyltrichlorostannane and the ligand in CH₃OH/Na/THF yielded an aqua complex of pseudostannatrane [LSnBu(H₂O)] (1_a), which was crystallized as its acetone solvate (i.e 1_a·Me₂CO). However, the same reactants yielded methanol complex [LSnBu(CH₃OH)] (1_b) when the reaction was carried out in the NaOCH₃/C₂H₅OH system. Similarly, the reaction of phenyltrichlorostannane and the ligand under these solvent systems yielded pseudostannatranes, i.e., an aqua complex [LSnPh(H₂O)] (2_a) and a methanol complex [LSnPh(CH₃OH)] (2_b) (where 2_a was crystallized as 2_a·Me₂CO). The reaction of tin tetrachloride and the ligand in the Et₃N/THF system resulted in the formation of pseudostannatrane [LHSnCl₂] (3). A similar product was isolated as its triethylamine solvate (3·NEt₃) due to the disproportion reaction when PhSnCl₃ was reacted with the ligand in the Et₃N/C₆H₅CH₃ system, which demonstrates the first report on the reverse Kocheshkov reaction in pseudostannatranes. The experimental findings on the formation of 3·NEt₃ due to the reverse Kocheshkov reaction have been corroborated with ¹¹⁹Sn NMR spectroscopy and density functional calculations that provide insightful information about the underlying details of the reaction route.

中文翻译：

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具有不对称[4.4.3.01,5]十三烷笼的单核伪金刚烷类：苯基伪金刚烷类化合物逆Kocheshkov反应的实验和理论方面。

已经报道了具有[4.4.3.0 ^1,5 ]十三烷笼的单核拟锡烷的合成方案，结构方面和光谱方面。使具有不对称臂的三脚形配体N（CH ₂ CH ₂ OH）{CH ₂（2- t -Bu-4-Me-C ₆ H ₂ OH）} ₂（H ₃ L）与正丁基三氯锡烷，苯基三氯锡烷反应，和下不同溶剂体系四氯化锡以获得pseudostannatranes（1 - 3）。的反应Ñ -butyltrichlorostannane和在CH配体₃OH / Na / THF生成拟锡金烷[LSnBu（H ₂ O）]（1 _a）的水配合物，将其结晶为丙酮溶剂化物（即1 _a ·Me ₂ CO）。然而，相同的反应物，得到甲醇络合物[LSnBu（CH ₃ OH）]（1 _b）当反应是在的NaOCH进行₃ / C ₂ H ^ ₅ OH系统。类似地，在这些溶剂系统下，苯基三氯锡烷与配体的反应产生了假金刚烷类，即水络合物[LSnPh（H ₂ O）]（2 _a）和甲醇络合物[LSnPh（CH ₃ OH）]（2 _b）（其中2 _a结晶为2 _a ·Me ₂ CO）。四氯化锡与配体在Et ₃ N / THF系统中的反应导致假锡金烷[LHSnCl ₂ ]的形成（3）。当PhSnCl ₃与Et ₃ N / C ₆ H ₅ CH _3中的配体反应时，由于歧化反应，分离出相似的产物作为其三乙胺溶剂化物（3 · NEt ₃）。系统，展示了有关伪锡烷的反Kocheshkov反应的第一份报告。¹¹⁹ Sn NMR光谱和密度泛函计算证实了由于逆Kocheshkov反应而形成3 · NEt ₃的实验结果，这些信息提供了有关反应路线基本细节的深刻信息。