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Herein, we report the synthesis of a series of heteroleptic magnesium complexes stabilized with the scorpionate ligand tris(2-pyridylthio)methanide (Tptm). The compounds of the general formula [Mg(Tptm)(X)] (<b>1-X</b>; X = Cl, Br, I) were obtained via protonolysis reaction between the proligand and selected Grignard reagents. Attempts to isolate the potassium derivative K(Tptm) lead to decomposition of Tptm and formation of the alkene (C₅H₄N-S)₂C=C(C₅H₄N-S)₂, and this degradation was also modelled using DFT methods. Compound <b>1-I</b> was treated with K(CH₂Ph), affording the degradation product [Mg(Bptm)₂] (<b>2</b>; Bptm = {CH(S-C₅NH₃)₂}⁻). We analyzed and quantified the steric properties of the Tptm ligand using the structural information of the compounds obtained in this study paired with buried volume calculations, also adding the structural data of HTptm and its CF₃-substituted congener (HTptm^CF3). These studies highlight the highly flexible nature of this ligand scaffold and its ability to stabilize various coordination motifs and geometries, which is a highly desirable feature in the design of novel organometallic reagents and catalysts.