Oxidation of [Ir(η5-C5Me5)(C8H4S8)] and crystal structures of [IrI(η5-C5Me5(C8H4S8)](I3) and [IrI(η5-C5Me5)(C8H4S8)](I3)1/2(I7)1/2

Abstract [Ir(η 5 -C 5 Me 5 )(C 8 H 4 S 8 )] ( 1 ) [ C 8 H 4 S 8 2 -  = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithionate(2−)] was reacted with iodine in dichloromethane to afford one-electron- and two-electron-oxidized species [IrI(η 5 -C 5 Me 5 )(C 8 H 4 S 8 )] ( 2 ), [IrI(η 5 -C 5 Me 5 )(C 8 H 4 S 8 )](I 3 ) ( 3 ) and [IrI(η 5 -C 5 Me 5 )(C 8 H 4 S 8 )](I 5 ) ( 4 ). The oxidized species exhibit electrical conductivities of (1.1–5.0) × 10 −6  S cm −1 measured for compacted pellets at room temperature. The X-ray crystal structures of the two-electron-oxidized complexes 3 and 4 revealed the Ir–I bonds for both of them and the presence of I 3 - for 3 and I 3 - and I 7 - ions for 4 as the counter anions. They have many S–S and S–I non-bonding contacts to form two-dimensional molecular interaction sheets in the solid state.