TRANS-IR(PPH3)2(CO)(NHAR) COMPLEXES - THEIR SYNTHESES, CHARACTERIZATION, AND REACTIONS WITH CO

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-C6H3Me2)].0.5C6H6: C48H43IrNOP2; triclinic P1BAR, a = 9.072(2) angstrom, b = 11.667(2) angstrom, c = 21.133(4) angstrom, alpha = 88.74(2)-degrees, beta = 81.24(2)-degrees, gamma = 73.74(2)-degrees, V = 2121.9(7) angstrom3, Z = 2, R(F) = 0.035, and R(w)(F) = 0.049 for 5038 (F > 5sigma(F)) reflections.