Preparation and Oxidation of Pt(II)Complexes Containing Both C-Deprotonated 2-Phenylpyridine(ppy~-)and a Sulfur-Rich Dithiolate Ligand and X-ray Crystal Structure of [NBu_4~n][Pt(ppy)(C_8H_4S8)]

摘要

[NEt4][Pt(ppy)(C_3S_5)](ppy~ = C-deprotonated 2-phenylpyridine(-);C3S52~ = 4,5-disulfanyl-l,3-dithiole-2-thionate(2-)),[NEt_4]-,[NBu"4][Pt(ppy)(C_8H_4S_8)](C_8H_4S_8~(2-)= 2-{(4,5-ethylenedithio)-l,3-dithiole-2-ylidene}-l,3-di-thiole-4,5-dithiolate(2-))and [NEt4][Pt(ppy)(C_(10)-C_6S_8)](C_(10)-C_6S_8~(2-)= 2-{bis(decylthio)-l,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithiolate(2-))were prepared.They showed an intense electronic absorption band due to an intramolecular mixed metal/dithiolate ligand-to-ppy ligand charge transfer transition,which is somewhat sensitive to the solvent.The complexes exhibited first oxidation potentials of-0.27 to +0.02 V(vs Ag/Ag~+)due to the dithiolate li-gand-centered oxidation.They were oxidized by TCNQ and iodine to afford [Pt(ppy)(L)] and [Pt(ppy)(L)](11.0-4.2)(L = C_3S_5~(2-),C_8H_4S_8~(2-),and C_(10)-C_6S_8~(2-))-Electrical conductivities of the oxidized C_8H_4S_8-and C_(10)-C_6S_8-species measured for compacted pellets at room temperature were 6.2 X 10~(-6)-7.8 X 10~(-3)S cm~(-1),while those of the oxidized C_3S_5-species were very low [(3.8-6.2)X 10~(-9)S cm~(-1)].The X-ray crystal structure of [NBu_4~n][Pt(ppy)(C_8H_4S_8)] was clarified.