Preparation of a series of dinuclear Ir(III) and Ir(II) complexes containing bridging thiolate ligands

Article abstract of DOI:10.1016/s0020-1693(97)05598-9

Reactions of [Cp*IrCl(μ-Cl)₂IrCp*Cl] (Cp* = η⁵-C₅Me₅) with RSH in CH₂Cl₂ at room temperature afforded two types of thiolatebridged dinuclear Ir(III) complexes, [Cp*IrCl(μ-SR)₂IrCp*Cl] (2; R = Pr¹, Cy, CH₂Ph; Cy = cyclohexyl) or [Cp*Ir(μ-SEt)₃IrCp*]Cl, depending upon the nature of the substituent R. Reduction of 2 (R = Pr¹ (2a), Cy) with excess Na-Hg in THF resulted in the formation of the dinuclear Ir(II) complexes [Cp*Ir(μ-SR)₂IrCp*] (3). X-ray diffraction studies were undertaken for 2a and 3b (R = Cy) to determine their detailed structures. 2a: C₂₆H₄₄Cl₂S₂Ir₂, space group C2/c, a = 21.255(8), b = 8.606(6), c = 17.788(6) A?, β = 118.39(2)°, Z = 4. 3b: C₃₂H₅₂S₂Ir₂, space group P2/n, a = 8.912(6), b = 11.224(6), c = 16.496(6) A?, β = 97.78(4)°, Z=2. Complexes 3 reacted with CF₃COOH to give the cationic Ir(III) complexes having a bridging hydride ligand [Cp*Ir(μ-H) (μ-SR)₂IrCp*] [OCOCF₃].