Abstract : Platinum(II) aryl thiolate complexes formulated as (P2)Pt(SAr)2 are prepared from the chelating bis(diphenylphosphino)dimethyltetrathiafulvalene (P2), with aryl thiolate ligands (SAr), such as benzenethiolate (BT) and 3,5-dimethylbenzenethiolate (DMBT). The structurally characterized neutral (P2)Pt(SAr)2 complexes afford, upon oxidation with TCNQF4, dicationic bimetallic Pt(II) complexes formulated as [(P2)Pt(μ-SAr)2Pt(P2)]2+, characterized by a flexible {Pt2(μ-SAr)2} square motif. The magnetic properties of the TCNQF4radical dot− salts of these bimetallic Pt(II) complexes are determined from susceptibility measurements and a tentative rationale for the formation of such {Pt2(μ-SAr)2} square complexes are provided, based on an original oxidative dimerization process.