Synthesis, structures, and oxidation of iridium(III) alkyl compounds containing thiolate and dithiolate ligands

Treatment of [Ir(dtbpy){CH2CMe2Cc6H4(Ir-Cc)}(C6H4tBu-2)] (1) (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) with the dichalcogenides R2Q2 in refluxing toluene afforded the chalcogenolate-bridged dinuclear complexes [Ir(dtbpy)-{CH2CMe 2C66H4(Ir-Cc)}] 2(μ-QR)2 [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH2CMe2-Cc6H4(Ir-Cc)}(CH2CMe2Ph)] and p-tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH2CMe 2Cc6H4(Ir-Cc)}] 2(μ-SpTol)2 (4). Treatment of [Ir(dtbpy)(CH 2CMe2Ph)Cl]2(μ-Cl)2 with Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na2(S∧S) afforded [Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5) and [Ir(dtbpy)-(CH2CMe2Ph)(S∧S)]2 {S∧S2- = maleonitriledithiolate (6), toluene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf- = triflate) resulted in dimerization of the bdt2- ligand by S-S bond formation and the isolation of [Ir2(dtbpy)2(CH 2Me2Ph)2{(bdt)2}][OTf]2 (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined. KGaA, 2008.