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

Abstract

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)(PR₃)}₂](R = C₆H₁₁3, o-MeC₆H₄4 or p-FC₆H₄5). When the bulky phosphite P(OC₆H₄Bu^t-o)₃ was used as phosphorus ligand the orthometallated complex trans-[{[graphic omitted]H₃Bu^t-o)(OC₆H₄Bu^t-o)₂]}₂]6 was obtained. The crystal structures of 1 and 6, have been determined by X-ray diffraction methods.