Synthesis and characterization of chiral bis(aminato)iridate(I) and aminato-bridged iridium(I) complexes

The two dinuclear Ir-I complexes [Ir-2(mu-Cl)(2) ((R)-(S)-PPF-PPh2}(2)] (1: (R)-(S)-PPF-PPh2 = (S)-1-(diphenylphosphino)-2-[(R)-1-(diphenylphosphino)e thyl]ferrocene and [Ir-2(mu-Cl)(2)((R)-binap}(2)] (3; (R)-binap = (R)-[1,1' -binaphthalene]-2,2'-diylbis[diphenylphosphine]) smoothly react with 4 equi v. of the lithium salt of aniline to afford the new bis(anilido)iridate(I) (= bis(benzenaminato)iridate(1-)) complexes Li[Ir(NHPh)(2)((R)-(S)-PPF-PPh2 }] (4) and Li[Ir(NHPh)(2){(R)-binap)} (5). respectively. The anionic comple xes 4 and 5 react upon protonolysis to give the dinuclear aminato-bridged d erivatives [Ir-2(mu-NHPh)(2)[(R)-(S)-PPF-PPh2}(2)] (6) and [Ir-2(mu-NHPh)(2 ){(R)-binap)(2)] (7), which were characterized by X-ray crystallography. No ne of the new complexes 4-7 shows catalytic activity in the hydroamination of olefins.