trans-Ir(PPh3)2(CO) (NHAr) complexes: Their syntheses, characterization, and reactions with CO

Article abstract of DOI:10.1021/om00017a035

The synthesis and characterization of Ir(I)-arylamido complexes, trans-Ir(PPh₃)₂(CO)(NHAr), where Ar = C₆H₅, p-C₆H₄Me, o-C₆H₄Me, 3,5-C₆H₃Me₂, 2,6-C₆H₃Me₂, p-C₆H₄Cl, and p-C₆H₄NO₂, are described. These complexes, except trans-Ir(PPh₃)₂(CO) [NH(p-C₆H₄NO₂)], undergo rapid reactions with CO at atmospheric pressure and ambient temperatures. For the complexes containing the sterically bulky NH(3,5-C₆H₃Me₂) and NH(2,6-C₆H₃Me₂) ligands, the CO reactions generate carbamoyl moieties, which result from an insertion of CO into the iridium-nitrogen bond. The end products in the reactions of the other arylamido complexes with CO contain orthometalated carbamoyl moieties, with the generation of hydrido-Ir(III) centers. Intermediates leading to the formation of the orthometalated complexes are discussed. Crystal data for trans-Ir(PPh₃)₂(CO)[NH(3,5-C₆H ₃Me₂)]·0.5C₆H₆: C₄₈H₄₃IrNOP₂; triclinic P1, a = 9.072(2) A?, b = 11.667(2) A?, c = 21.133(4) A?, α = 88.74(2)°, β = 81.24(2)°, γ = 73.74(2)°, V = 2121.9(7) A?³, Z = 2, R(F) = 0.035, and R_w(F) = 0.049 for 5038 (F > 5σ(F)) reflections.