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

[Ir(η5-C5Me5)(C8H4S8)] (1) [C8H4S82- = 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(η5-C5Me5)(C8H4S8)] (2), [IrI(η5-C5Me5)(C8H4S8)](I3) (3) and [IrI(η5-C5Me5)(C8H4S8)](I5) (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 I3- for 3 andI3-andI7- 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.

Graphical abstract[Ir(η5-C5Me5)(C8H4S8)] [C8H4S82- = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithionate(2−)] was oxidized by iodine to afford one-electron-oxidized [IrI(η5-C5Me5)(C8H4S8)] and two-electron-oxidized species [IrI(η5-C5Me5)(C8H4S8)](I3) and [IrI(η5-C5Me5)(C8H4S8)](I5). These 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 were determined.Figure optionsDownload full-size imageDownload as PowerPoint slide