Synthesis, Structures, and Oxidation of Iridium(III) Alkyl Compounds Containing Thiolate and Dithiolate Ligands

Treatment of [Ir(dtbpy){CH 2 CMe 2 C c 6 H 4 ( Ir–C c )}(C 6 H 4 t Bu‐2)] ( 1 ) (dtbpy = 4,4′‐di‐ tert ‐butyl‐2,2′‐bipyridyl) with the dichalcogenides R 2 Q 2 in refluxing toluene afforded the chalcogenolate‐bridged dinuclear complexes [Ir(dtbpy) {CH 2 CMe 2 C c 6 H 4 ( Ir–C c )}] 2 (μ‐QR) 2 [RQ = p TolS ( 2 ), PhSe ( 3 )]. Similarly, heating a solution of [Rh(dtbpy){CH 2 CMe 2 C c 6 H 4 ( Ir–C c )}(CH 2 CMe 2 Ph)] and p ‐tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH 2 CMe 2 C c 6 H 4 ( Ir–C c )}] 2 (μ‐S p Tol) 2 ( 4 ). Treatment of [Ir(dtbpy)(CH 2 CMe 2 Ph)Cl] 2 (μ‐Cl) 2 with Na(Sxyl) (xyl = 2,6‐dimethylphenyl) and Na 2 (S ∧ S) afforded [Ir(dtbpy)(CH 2 CMe 2 Ph)(Sxyl) 2 ] 2 ( 5 ) and [Ir(dtbpy)(CH 2 CMe 2 Ph)(S ∧ S)] 2 {S ∧ S 2– = 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 bdt 2– ligand by S–S bond formation and the isolation of [Ir 2 (dtbpy) 2 (CH 2 Me 2 Ph) 2 {(bdt) 2 }][OTf] 2 ( 9 ). The solid‐state structures of compounds 2 , 3 , 4 , 7 , and 9 were determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)