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)center dot 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)center dot 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 center dot 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 center dot NEt3 due to the reverse Kocheshkov reaction have been corroborated with Sn-119 NMR spectroscopy and density functional calculations that provide insightful information about the underlying details of the reaction route.