Preparation, structure and reactivity of dinuclear aminothiolate-bridged iridium complexes

Addition of the aminothiolate HS(CH2)3NMe2 and potassium tert-butoxide to [{Ir(μ-Cl)(cod)}2] (cod = cycloocta-1,5-diene) afforded the aminothiolate-bridged complex [{Ir[μ-S(CH2)3NMe2](cod)}2] 1. This reacted with carbon monoxide to give the dinuclear tetracarbonyl complex [{Ir[μ-S(CH2)3NMe2](CO)2} 2] 2. The reaction of 1 with CO and phosphines or of 2 with phosphines provided the mixed-ligand complexes trans-[{Ir[μ-S(CH2)3NMe2](CO)(PR 3)}2] (R = C6H11 3, o-MeC6H4 4 or p-FC6H4 5). When the bulky phosphite P(OC6H4But-o)3 was used as phosphorus ligand the orthometallated complex trans-[{Ir[μ-S(CH2)3NMe2]H(CO)[P(OC 6H3But-o)(OC6H4Bu t-o)2]}2] 6 was obtained. The crystal structures of 1 and 6, have been determined by X-ray diffraction methods.