Properties of Pt(II) complexes with a sulfur-rich dithiolate ligand havingalkyl chains and of their oxidized species. The X-ray crystal structure of[NBu4n](2)[Pt{C6S8(C10H21)(2)}]

Reactions of [NBu4II](2)[PtCl4] with Na-2[C6S8R2] [C6S8R22- = {bis(alkylthi o)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithiolate(2-); R = C10H21, C14 H29 or C18H37] in methanol afforded [NBu4II](2)[Pt(C6S8R2)(2)]. The crystal structure of [NBu4n](2)[Pt{C6S8(C10H21)(2)}(2)] was determined by X-ray an alysis. The crystal packing structure consists of columns of anion units as sembled through the association of alkyl chains, where the metal-center uni ts are separated by the bulky cations. These complexes exhibit oxidation po tentials of -0.25 to +0.35 V vs. SCE. They were oxidized by bromine or iodi ne to yield essentially two-electron oxidized species [Pt(C6S8R2)(2)](0), w ith ligand-centered oxidation. The oxidized complexes (R = C10H21 and C14H2 9) exhibit electrical conductivities (sigma) of 1.4 x 10(-2) to 4.9 x 10(-2 ) S cm(-1) measured for compacted pellets at room temperature, while the ox idized species with R = C18H37 behaves as an insulator (sigma < 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 ref lectance spectra.