Treatment of [Ir(bpa)(cod)]+ complex + with a strong base (e.g., tBuO−) led to unexpected double deprotonation to form the anionic [Ir(bpa−2H)(cod)]− species −, via the mono-deprotonated neutral amido complex [Ir(bpa−H)(cod)] as an isolable intermediate. A certain degree of aromaticity of the obtained metal–chelate ring may explain the favourable double deprotonation. The rhodium analogue − was prepared in situ. The new species [M(bpa−2H)(cod)]− (M=Rh, Ir) are best described as two-electron reduced analogues of the cationic imine complexes [MI(cod)(Py-CH2-NCH-Py)]+. One-electron oxidation of − and − produced the ligand radical complexes . and .. Oxygenation of − with O2 gave the neutral carboxamido complex [Ir(cod)(py-CH2-N-CO-py)] via the ligand radical complex . as a detectable intermediate.