Open platinum aggregate frameworks with overhead dithiolate bridges

A convenient method has been developed to bring together two discrete moieties of [Pt2(μ-S)2(PPh3)4] to give an open Pt4 aggregate of Pt2···(spacer)···Pt2, as exemplified in the isolation of [(PPh3)4Pt2(μ-S)(μ-SRS)(μ-S)Pt2(PPh3)4](PF6)2 [R = m-CH2C6H4CH2, p-CH2C6H4CH2, CH2C10H6CH2, and CH2(C6H4)2CH2]. 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 Pt2 core, as given in [Pt2(μ-S-o-CH2C6H4-C6H4CH2S)(PPh3)4](PF6)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)

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