Preparation, Structure and Reactivity of Dinuclear Aminothiolate-bridged Iridium Complexes

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

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