Open Platinum Aggregate Frameworks with Overhead Dithiolate Bridges

A convenient method has been developed to bring together two discrete moieties of [Pt 2 (μ‐S) 2 (PPh 3 ) 4 ] to give an open Pt 4 aggregate of Pt 2 ··· (spacer) ··· Pt 2 , as exemplified in the isolation of [(PPh 3 ) 4 Pt 2 (μ‐S)(μ‐SRS)(μ‐S)Pt 2 (PPh 3 ) 4 ](PF 6 ) 2 [R = m ‐CH 2 C 6 H 4 CH 2 , p ‐CH 2 C 6 H 4 CH 2 , CH 2 C 10 H 6 CH 2 , and CH 2 (C 6 H 4 ) 2 CH 2 ]. The spacer is a dithiolate with an extended skeletal backbone formed from the alkylation of sulfide with a suitable dibromo‐organic compound. This synthetic methodology can tolerate a range of conformationally contrasting thiolate substituents with different chemical functionalities. Shorter or stereochemically more restrictive spacers could opt to be an intramolecular bridge over the Pt 2 core, as given in [Pt 2 (μ‐S‐ o ‐CH 2 C 6 H 4 ‐C 6 H 4 CH 2 S)(PPh 3 ) 4 ](PF 6 ) 2 . A few representative complexes have been characterized by single‐crystal X‐ray diffraction analysis.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)