Oxidative access to flexible {Pt2(μ-SAr)2} square motifs from platinum thiolato complexes with chelating diphosphine

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.