Mononuclear Pseudostannatranes Possessing Unsymmetrical [4.4.3.0^1,5]Tridecane Cage: Experimental and Theoretical Aspects of Reverse Kocheshkov Reaction in Phenyl Pseudostannatrane

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.