In the course of our investigations of the coordination chemistry of trivalent antimony (Sb) compounds, we studied heteronuclear complexes formed in reactions of the compounds RSb(pyS)(2) (R = pyS, Ph; pyS(-) = pyridine-2-thiolate) with [Pt(PPh3)(4)], i.e., complexes [(R)Sb(mu-pyS)(2) Pt(PPh3)] (R = pyS, 1; R = Ph, 2). The reaction of 1 with o-chloranil proceeds cleanly with elimination of 2,2'-dipyridyl disulfide and formation of the salt [(PPh3)Pt(mu-pyS)(2)Sb(mu-pyS)(2)Pt(PPh3)](+)[Sb(C6Cl4O2)(2)](-)(3(III)), which features the cation 3(+). The charge-neutral, unsymmetrically substituted compound [(PPh3)Pt(mu-pyS)(2)Sb(mu-pyS)(2)Pt(kappa S-pyS)] (4) can be accessed by the reaction of 3(+) with LipyS. The oxidation of 2 with o-chloranil furnishes the complex [(kappa-O,O-C6Cl4O2)PhSb(mu-pyS)(2)Pt(PPh3)] (5). The oxidation of 1 with PhICl2 afforded the paddlewheel-shaped complex [Sb(mu-pyS)(4)PtCl] (6). Moreover, compound 6 was obtained by the reaction of Sb(pyS)(3) with [PtCl(pyS)-(PPh3)]. The polarization of Pt-Sb bonds of compounds 1-6 was investigated by natural localized molecular orbital (NLMO) calculations, which suggest X- type ligand character (covalent Pt-Sb bonds) for 1 and 2, whereas the Sb ligand of 6 reflects Z-type character (dative Pt -> Sb bonds). In 3(+), 4, and 5, high contributions of the reverse, i.e., L-type (dative Pt <- Sb bonds), were observed. In conjunction with the results of NLMO analyses, Sb-121 Mossbauer spectroscopy proves that complexes 1-6 represent essentially trivalent Sb complexes with either a free lone pair (LP) at the Sb atom (1, 2, and 6) or LP character involved in L-type Pt <- Sb coordination (3(+), 4, and 5).