The compounds Pn (pyS) 3 ( Pn = P, As, Sb, Bi) were synthesized from the respective chloride ( Pn = P, As, Sb) or nitrate (Bi), pyridine-2-thiol (pySH) and triethylamine (NEt 3 ) as a supporting base in THF (P, Sb), CHCl 3 (As) or methanol (Bi). Sb(pyS) 3 was also obtained from the reaction of SbCl 3 with LipyS (prepared in situ ) in methanol. The compounds Sb(pyS) 2 Ph and Sb(pyS)Ph 2 were prepared in a one-pot reaction starting from SbCl 3 and SbPh 3 (1:1 ratio). Upon Cl/pyS substitution, the resulting reaction mixture allows for a facile separation of the products in hot hexane. P(pyS) 3 and As(pyS) 3 crystallize isostructurally to the reported structure of Sb(pyS) 3 with κ -S-bound pyS ligands. These crystal structures feature close Pn ··· Pn contacts which are most pronounced for the arsenic derivative. Bi(pyS) 3 adopts a different molecular structure in the solid state, which features two chelating ( κ 2 -S,N-pyS) ligands and a κ -S-bound ligand. The presence of N→Bi interactions between the nitrogen atom of the κ -S-pyS ligand and the Bi atom of another molecule renders this structure a polymer chain along the crystallographic b axis with Bi⋅⋅⋅Bi van-der-Waals contacts. The structures of this set of Pn (pyS) 3 compounds were also studied in solution using 1 H NMR spectroscopy, revealing equivalent pyS ligands in discrete Pn (pyS) 3 molecules. The molecular structure of Sb(pyS)Ph 2 was optimized by quantum chemical methods, and a comparison with the structures reported for the other Sb/pyS/Ph combinations reveals Sb(pyS) 2 Ph to feature the strongest Sb···N interactions with the κ -S-pyS ligand. The results of 1 H NMR spectroscopic investigations of the compounds Sb(pyS) x Ph 3– x ( x = 3–0) suggest the Ph protons in ortho position to be incorporated into intramolecular C–H···S contacts for x = 2 and 1. Natural localized molecular orbital (NLMO) calculations were employed in order to gain insights into the electronic situations of the Pn atoms and Pn –R bonds (R = S, C), especially for the effects caused by formal substitution of Pn in the compounds Pn (pyS) 3 and the ligand patterns in the compounds Sb(pyS) x Ph 3– x ( x = 3–0). For the latter series of compounds, the electronic situation of the Sb atom was further studied by 121 Sb Mössbauer spectroscopy, providing a correlation between the calculated electron density at Sb [ ρ (0)] and the experimentally observed isomer shift δ . The missing link between group 15 and group 13 metal compounds of the type M (pyS) 3 , compound Al(pyS) 3 , was synthesized in this work. In the solid state (confirmed crystallographically), the mer isomer of this tris -chelate complex with distorted octahedral Al coordination sphere was found. This coordination mode was confirmed for the solution state (CDCl 3 ) by 1 H and 13 C NMR spectroscopy at T = −40 °C.