α-Iminopyridine ligands L (2-(CHN(CH-2,4,6-Ph))CHN), L (2-(CHN(CH-2,4,6-Bu))CHN) and L (1,2-(CHN-2-CHN)CHCH) differing by the steric demand of the substituent on the imine CHN group and by the number of donating nitrogen atoms were utilized to initiate a Lewis base mediated ionization of SnCl in an effort to prepare ionic tin(II) species [L → SnCl][SnCl]. The reaction of L and L with SnCl led to the formation of neutral adducts [L → SnCl] (2) and [L → SnCl] (3). The preparation of the desired ionic compounds was achieved by subsequent reactions of 2 and 3 with an equivalent of SnCl or GaCl. In contrast, ligand L containing four donor nitrogen atoms showed the ability to ionize SnCl and also Sn(OTf), yielding [L → SnCl][SnCl] (7) and [L → Sn(HO)][OTf] (8). The study thus revealed that the reaction is dependent on the type of the ligand. The prepared complexes 4-8 together with the previously reported [{2-((CH)CN(CH-2,6-iPr))-6-CHO-CHN}SnCl][SnCl] (1) were tested as catalysts for the ROP of L-lactide, which could operate an activated monomer mechanism. Finally, a DFT computational study was performed to evaluate the steric and electronic properties of the ionic tin(II) species 1 and 4-8 together with their ability to interact with the L-lactide monomer.