Properties of Pt(ii) complexes with a sulfur‐rich dithiolate ligand having alkyl chains and of their oxidized species. The X‐ray crystal structure of [NBun4]2[Pt{C6S8(C10H21)2}]

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Abstract
Reactions of [NBu n 4 ] 2 [PtCl 4 ] with Na 2 [C 6 S 8 R 2 ] [C 6 S 8 R 2 2– = 2-{bis(alkylthio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithiolate(2–); R = C 10 H 21 , C 14 H 29 or C 18 H 37 ] in methanol afforded [NBu n 4 ] 2 [Pt(C 6 S 8 R 2 ) 2 ]. The crystal structure of [NBu n 4 ] 2 [Pt{C 6 S 8 (C 10 H 21 ) 2 } 2 ] was determined by X-ray analysis. The crystal packing structure consists of columns of anion units assembled through the association of alkyl chains, where the metal-center units are separated by the bulky cations. These complexes exhibit oxidation potentials of –0.25 to +0.35 V vs. SCE. They were oxidized by bromine or iodine to yield essentially two-electron oxidized species [Pt(C 6 S 8 R 2 ) 2 ] 0 , with ligand-centered oxidation. The oxidized complexes (R = C 10 H 21 and C 14 H 29 ) exhibit electrical conductivities (σ) of 1.4 × 10 –2 to 4.9 × 10 –2 S cm –1 measured for compacted pellets at room temperature, while the oxidized species with R = C 18 H 37 behaves as an insulator (σ < 10 –8 S cm –1 ). Electronic states and molecular interactions of the complexes in the solid state are discussed based on EPR, XPS, electronic absorption and reflectance spectra.

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