Salt elimination reactions between organopnictogen(III) dichlorides, RPnCl₂ [R¹ = 2,6-(Me₂NCH₂)₂C₆H₃, Pn = Sb (1), Bi (2); R² = 2,6-{MeN(CH₂CH₂)₂NCH₂}₂C₆H₃, Pn = Sb (3), Bi (4); R³ = 2,6-{O(CH₂CH₂)₂NCH₂}₂C₆H₃, Pn = Sb (5), Bi (6)] and 2 equivalents of KSC₆H₃Me₂-2,6 afforded the isolation of a series of new NCN-chelated monoorganopnictogen(III) bis(arylthiolates), RPn(SC₆H₃Me₂-2,6)₂ [R¹, Pn = Sb (7), Bi (8); R², Pn = Sb (9), Bi (10); R³, Pn = Sb (11), Bi (12)]. Compounds 7 and 8 are unstable upon exposure to a dry O₂ atmosphere and their aerobic decomposition yields the monoorganopnictogen(III) oxides, cyclo-[2,6-(Me₂NCH₂)₂C₆H₃Pn(μ-O)]₂ [Pn = Sb (13), Bi (14)] with concomitant formation of the corresponding disulfide, ArS–SAr (Ar = C₆H₃Me₂-2,6). The oxidative addition of elemental sulfur or selenium to 7 undergoes a similar reaction path and gives stable heterocyclic species cyclo-[2,6-(Me₂NCH₂)₂C₆H₃Sb(μ-E)]₂ [E = S (15), Se (16)]. The reaction of 12 with I₂ (1 : 1 molar ratio) gives the diiodide [2,6-{O(CH₂CH₂)₂NCH₂}₂C₆H₃]BiI₂ (17), along with the S–S oxidative coupling by-product, ArS–SAr. The use of an excess of iodine affords the crystallization of a 2 : 1 iodine adduct of 17 (17·0.5I₂), built through halogen bonding. All new compounds were characterized by multinuclear NMR spectroscopy and ESI-MS as well as single crystal X-ray diffraction (except compounds 9 and 10).